Method of making indeno-fused naphthol materials

ABSTRACT

The present invention relates to a method of making indeno-fused naphthol materials, that involves, with some embodiments, forming an indanone acid intermediate, which can be represented by the following general Formula V, 
     
       
         
         
             
             
         
       
     
     With Formula V, m is from 0 to 4, and R 1  for each m, R g  and R h  can each be independently selected from, for example, hydrogen and hydrocarbyl. The present invention also relates to a method of making an indeno-fused naphthopyran that involves an indanone acid intermediate synthetic route.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority of U.S. ProvisionalPatent Application No. 61/459,617, filed Dec. 16, 2010, all of whichdocument is hereby incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to a method of making indeno-fusednaphthol materials and related materials, such as photochromicindeno-fused naphthopyrans, that involves forming an indanone acidintermediate.

BACKGROUND OF THE INVENTION

Indeno-fused naphthol materials, including ethers and esters ofindeno-fused naphthols, have many uses, such as intermediates in thesynthesis of photochromic compounds and materials, such as indeno-fusednaphthopyrans. Photochromic materials, such as indeno-fusednaphthopyrans, in response to certain wavelengths of electromagneticradiation (or “actinic radiation”), typically undergo a transformationfrom one form or state to another form, with each form having acharacteristic or distinguishable absorption spectrum associatedtherewith. Typically, upon exposure to actinic radiation, manyphotochromic materials are transformed from a closed-form, whichcorresponds to an unactivated (or bleached, e.g., substantiallycolorless) state of the photochromic material, to an open-form, whichcorresponds to an activated (or colored) state of the photochromicmaterial. In the absence of exposure to actinic radiation, suchphotochromic materials are reversibly transformed from the activated (orcolored) state, back to the unactivated (or bleached) state.Compositions and articles, such as eyewear lenses, that containphotochromic materials or have photochromic materials applied thereto(e.g., in form of a photochromic coating composition) typically displaycolorless (e.g., clear) and colored states that correspond to thecolorless and colored states of the photochromic materials containedtherein or applied thereto.

Indeno-fused naphthol materials are typically prepared by a syntheticscheme involving the reaction of a benzophenone with a dialkylsuccinate, which is typically referred to as a Stobbe reaction route.When unsymmetrical benzophenones are used, a mixture of indeno-fusednaphthol materials typically results from the Stobbe reaction route. Themixture of indeno-fused naphthols typically must be separated so as toisolate the desired indeno-fused naphthol. The isolated indeno-fusednaphthol can then be used in subsequent reactions (e.g., in thesynthesis of photochromic indeno-fused naphthopyrans). The separationand isolation steps generally result in significantly reduced yieldsrelative to the desired indeno-fused naphthol materials.

Some photochromic materials, such as photochromic indeno-fusednaphthopyrans can be expensive, and in light of economic considerations,reducing the costs associated with synthesizing such materials istypically desirable.

It would be desirable to develop new methods of making indeno-fusednaphthol materials. In addition, it would be desirable that such newlydeveloped methods provide improved yields, and economic benefitsrelative to previous synthetic methods.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided a method ofmaking an indeno-fused naphthol material represented by the followingFormula I,

With reference to Formula I, m and n are each independently selectedfrom 0 to 4. With further reference to Formula I, R¹ for each m, and R²for each n, are in each case independently selected from hydrocarbyloptionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—,—S(O)—, —SO₂—, —N(R₁₁′)— where R₁₁′ is selected from hydrogen,hydrocarbyl or substituted hydrocarbyl, and combinations of two or morethereof; substituted hydrocarbyl optionally interrupted with at leastone of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N(R₁₁′)— where R₁₁′ isselected from hydrogen, hydrocarbyl or substituted hydrocarbyl, andcombinations of two or more thereof; halogen; cyano; and —N(R₁₁′)R₁₂′,wherein R₁₁′ and R₁₂′ are each independently selected from hydrogen,hydrocarbyl or substituted hydrocarbyl, or R₁₁′ and R₁₂′ together forman aliphatic and/or aromatic ring structure (e.g., a single ring,polycyclic ring, or fused ring structure) optionally including at leastone heteroatom. The R^(g) and R^(h) groups of Formula I are eachindependently selected from, hydrogen; hydrocarbyl optionallyinterrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—,—SO₂—, and —N(R₁₁′)— where R₁₁′ is selected from hydrogen, hydrocarbylor substituted hydrocarbyl; and substituted hydrocarbyl optionallyinterrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, and—N(R¹¹′)— where R₁₁′ is selected from hydrogen, hydrocarbyl orsubstituted hydrocarbyl; or R^(g) and R^(h) together form a ringstructure optionally including at least one heteroatom.

The method of making the indeno-fused naphthol material represented bythe Formula I comprises,

(a) reacting an alkyl benzene represented by Formula II with maleicanhydride, thereby forming a succinic acid substituted intermediaterepresented by Formula III,

The method of the present invention further comprises,

(b) converting the succinic acid substituted intermediate represented byFormula III to a succinic anhydride substituted intermediate representedby Formula IV,

The method of the present invention further comprises,

(c) converting the succinic anhydride substituted intermediaterepresented by

Formula IV to an indanone acid intermediate represented by Formula V,

The method of the present invention further comprises,

(d), reacting the indanone acid intermediate represented by Formula Vwith a nucleophile represented by Formula VI to form a substitutedindanone intermediate represented by at least one of Formula VIIa,Formula VIIb and Formula VIIc,

wherein M represents a counterion comprising a metal selected from Mg,Li, Cu and combinations thereof,

The method of the present invention, still further comprises,

(e) converting the substituted indanone intermediate represented by atleast one of Formula VIIa, Formula VIIb and Formula VIIc to theindeno-fused naphthol represented by Formula I.

With Formulas II, V, VI, VIIa, VIIb, and VIIc, m, R¹ n, R², R^(g), andR^(h) are in each case independently selected from those values, ranges,and groups as described above and further herein with reference toFormula I. Alternatively, one or more of R¹, R², R^(g), and R^(h) can ineach case independently represent one or more precursors of the thosegroups as described above and further herein with reference to FormulaI.

In accordance with the present invention, there is further provided amethod of making an indeno-fused naphthopyran represented by thefollowing Formula XI,

With the indeno-fused naphthopyran represented by Formula XI, m, R¹, n,R², R^(g), and R^(h) are in each case independently selected from thosevalues, ranges, and groups as described above and further herein withreference to Formula I, or in each case independently represent one ormore precursors of the those groups as described above and furtherherein with reference to Formula I.

The B and B′ groups of the indeno-fused naphthopyran represented byFormula XI are each independently selected from unsubstituted aryl,substituted aryl, unsubstituted heteroaryl, substituted heteroaryl,polyalkoxy, and polyalkoxy having a polymerizable group. Alternatively,B and B′ taken together form a ring structure selected fromunsubstituted fluoren-9-ylidene, substituted fluoren-9-ylidene,saturated spino-monocyclic hydrocarbon ring, saturated spiro-bicyclichydrocarbon ring, and spiro-tricyclic hydrocarbon ring.

The method of making the indeno-fused naphthopyran represented byFormula XI, involves forming the indeno-fused naphthol materialrepresented by Formula I as described above, and reacting theindeno-fused naphthol material represented by Formula I with a propargylalcohol represented by the following Formula XI,

With the propargyl alcohol represented by Formula XII, B and B′ are eachselected from those groups as described above and further herein withregard to Formula XI, or in each case independently represent one ormore precursors of the those groups as described above and furtherherein with reference to Formula XI.

DETAILED DESCRIPTION OF THE INVENTION

As used herein and in the claims, the term “actinic radiation” meanselectromagnetic radiation that is capable of transforming a photochromicmaterial from one form or state to another.

As used herein and in the claims, the term “photochromic” means havingan absorption spectrum for at least visible radiation that varies inresponse to absorption of at least actinic radiation. Further, as usedherein the term “photochromic material” means any substance that isadapted to display photochromic properties, i.e. adapted to have anabsorption spectrum for at least visible radiation that varies inresponse to absorption of at least actinic radiation, and which,includes at least one photochromic compound.

As used herein and in the claims, molecular weight values of polymers,such as weight average molecular weights (Mw) and number averagemolecular weights (Mn), are determined by gel permeation chromatographyusing appropriate standards, such as polystyrene standards.

As used herein and in the claims, polydispersity index (PDI) valuesrepresent a ratio of the weight average molecular weight (Mw) to thenumber average molecular weight (Mn) of the polymer (i.e., Mw/Mn).

As used herein and in the claims, recitations of “linear or branched”groups, such as linear or branched alkyl, are understood to include: amethylene group or a methyl group; groups that are linear, such aslinear C₂-C₂₀ alkyl groups; and groups that are appropriately branched,such as branched C₃-C₂₀ alkyl groups.

As used herein and in the claims, the term “halo” and similar terms,such as halo group, halogen, and halogen group means F, Cl, Br and/or I,such as fluoro, chloro, bromo and/or iodo.

Unless otherwise indicated, all ranges or ratios disclosed herein are tobe understood to encompass any and all subranges or subtatios subsumedtherein. For example, a stated range or ratio of “1 to 10” should beconsidered to include any and all subranges between, (and inclusive of)the minimum value of 1 and the maximum value of 10; that is, allsubranges or subratios beginning with a minimum value of 1 or more andending with a maximum value of 10 or less, such as but not limited to, 1to 6.1, 3.5 to 7.8, and 5.5 to 10.

As used herein and in the claims, unless otherwise indicated, the symbol“Δ” means heat or thermal energy, such as heat introduced into and/orretained within a chemical reaction.

As used herein and in the claims, the term “precursor” and relatedterms, such as “precursors” with regard to the various groups, forexample, R¹, R², R^(g), R^(h), B and B′, of the compounds andintermediates described herein, for example, the indeno-fused naphtholsrepresented by Formula I and the indeno-fused naphthopyrans representedby Formula XI, means a group that can be converted in one or more stepsto the final or desired group. For purposes of non-limitingillustration: a precursor of a hydroxyl group (—OH) includes, but is notlimited to, a carboxylic acid ester group (—OC(O)R where R is hydrogenor an optionally substituted hydrocarbyl); and a precursor of acarboxylic acid ester group (—OC(O)R) includes, but is not limited to, ahydroxyl group (—OH), which can be reacted, for example, with acarboxylic acid halide, such as acetic acid chloride (or acetylchloride).

As used herein and in the claims, unless otherwise indicated,left-to-right representations of linking groups, such as divalentlinking groups, are inclusive of other appropriate orientations, suchas, right-to-left orientations. For purposes of non-limitingillustration, the left-to-right representation of the divalent linkinggroup —C(O)O—, is inclusive of the right-to-left representation thereof,—O(O)C—.

As used herein and in the claims, the articles “a,” “an,” and “the”include plural referents unless otherwise expressly and unequivocallylimited to one referent.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be under stood asmodified in all instances by the term “about.”

The method of the present invention involves making an indeno-fusednaphthol, material represented by Formula I. The R¹, R², R^(g) and R^(h)groups of the indeno-fused naphthol material represented by Formula I,can in each case be selected from hydrocarbyl, and substitutedhydrocarbyl.

As used herein and in the claims the term “hydrocarbyl” and similarterms, such as “hydrocarbyl substituent,” means: linear or branchedC₁-C₂₀ alkyl (e.g., linear or branched C₁-C₁₀ alkyl); linear or branchedC₂-C₂₀ alkenyl (e.g., linear or branched C₂-C₁₀ alkenyl); linear orbranched C₂-C₂₀ alkynyl (e.g., linear or branched C₂-C₁₀ alkynyl);C₃-C₁₂ cycloalkyl (e.g., C₃-C₁₀ cycloalkyl); C₃-C₁₂ heterocycloalkyl(having at least one hetero atom in the cyclic ring); C₅-C₁₈ aryl(including polycyclic aryl groups) (e.g., C₅-C₁₀ aryl); C₅-C₁₈heteroaryl (having at least one hetero atom in the aromatic ring); andC₆-C₂₄ aralkyl (e.g., C₆-C₁₀ aralkyl).

Representative alkyl groups include but are not limited to methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl. Representativealkenyl groups include but are not limited to vinyl, allyl and propenyl.Representative alkynyl groups include but are not limited to ethynyl,1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representativecycloalkyl groups include but are not limited to cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl substituents.Representative heterocycloalkyl groups include but are not limited totetrahydrofuranyl, tetrahydropyranyl and piperidinyl. Representativearyl groups include but are not limited to phenyl and naphthyl.Representative heteroaryl groups include but are not limited to furanyl,pyranyl and pyridinyl. Representative aralkyl groups include but are notlimited to benzyl, and phenethyl.

The term “substituted hydrocarbyl” as used herein and in the claimsmeans a hydrocarbyl group in which at least one hydrogen thereof hasbeen substituted with a group that is other than hydrogen, such as, butnot limited to, halo groups, hydroxyl groups, ether groups, thiolgroups, thio ether groups, carboxylic acid groups, carboxylic acid estergroups, phosphoric acid groups, phosphoric acid ester groups, sulfonicacid groups, sulfonic acid ester groups, nitro groups, cyano groups,hydrocarbyl groups (e.g., alkyl, alkenyl, alkynyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl, and aralkyl groups), and aminegroups, such as —N(R₁₁′)(R₁₂′) where R₁₁′ and R₁₂′ are eachindependently selected from hydrogen, hydrocarbyl and substitutedhydrocarbyl.

The term “substituted hydrocarbyl” is inclusive of halohydrocarbyl (orhalo substituted hydrocarbyl) substituents. The term “halohydrocarbyl”as used herein and in the claims, and similar terms, such as halosubstituted hydrocarbyl, means that at least one hydrogen atom of thehydrocarbyl (e.g., of the alkyl, alkenyl, alkynyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl, and aralkyl groups) is replaced witha halogen atom selected from chlorine, bromine, fluorine and iodine. Thedegree of halogenation can range from at least one hydrogen atom beingreplaced by a halogen atom (e.g., a fluoromethyl group) to fullhalogenation (perhalogenation) in which all replaceable hydrogen atomson the hydrocarbyl group have been replaced by a halogen atom (e.g.,trifluoromethyl or perfluoromethyl). Correspondingly, the term“perhalohydrocarbyl group” as used herein and in the claims means ahydrocarbyl group in which all replaceable hydrogens have been replacedwith a halogen. Examples of perhalohydrocarbyl groups include, but arenot limited to, perhalogenated phenyl groups and perhalogenated alkylgroups.

The hydrocarbyl and substituted hydrocarbyl groups from which R¹, R²,R^(g), and R^(h) can each be selected, can in each case be independentlyand optionally interrupted with at least one of —O—, —S—, —C(O)—,—C(O)O—, —S(O)—, —SO₂—, —N(R₁₁′)—. As used herein and in the claims, byinterrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—,—SO₂—, —N(R₁₁′)—, means that at least one carbon of, but less than allof the carbons of, the hydrocarbyl group or substituted hydrocarbylgroup, is in each case independently replaced with one of the reciteddivalent non-carbon linking groups. The hydrocarbyl and substitutedhydrocarbyl groups can be interrupted with two, or more of the aboverecited linking groups, which can be adjacent each other or separated byone or more carbons.

The various groups of the indeno-fused naphthol materials, intermediatesand indeno-fused naphthopyrans prepared and used in accordance with themethods of the present invention, will be described in further detailherein.

The method of making or synthesizing the indeno-fused naphtholrepresented by Formula I, according to the present invention, involvesforming a succinic acid substituted intermediate represented by FormulaIII, by reacting an alkyl benzene represented by Formula II with maleicanhydride. The reaction is typically conducted in the presence of a freeradical generator, such as a peroxide, and under appropriate conditions,such as with reflux, as represented in the following Scheme 1.

The peroxide of Scheme-1 is typically a bishydrocarbyl peroxiderepresented by the formula, R^(a)—O—O—R^(b), in which the R^(a) andR^(b) groups can each be independently selected from hydrocarbyl andsubstituted hydrocarbyl, such as linear or branched C₁-C₁₀ alkyl orlinear or branched C₁-C₅ alkyl (e.g., methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, and tert-butyl). With some embodimentsof the present invention, R^(a) and R^(b) of the peroxide of Scheme 1are each selected from tert-butyl. The reflux can be conducted underappropriated conditions, including, for example reduced pressure,ambient pressure, and/or elevated pressure. Typically, the reflux underwhich the succinic acid substituted intermediate represented by FormulaIII is formed, is conducted under conditions of ambient pressure (e.g.,approximately 1 atm), under an inert atmosphere (e.g., under a nitrogensweep), and elevated temperature, such as from 50° C. to 200° C., orfrom 60° C. to 180° C., or from 80° C. to 150° C.

The alkyl benzene represented by Formula II can be used as both areagent and a solvent in the reaction represented by Scheme 1, and/or aseparate non-reactive solvent can be present. Typically, aftercompletion of the reaction, solvent and excess alkyl benzene, ifpresent, is removed by reduced pressure stripping, leaving crudesuccinic acid substituted intermediate represented by Formula III withinthe reaction vessel. The crude succinic acid substituted intermediaterepresented by Formula III can be further isolated or otherwise purifiedin accordance with art recognized methods, or used in its crude form inthe next step of the synthetic sequence.

In the next step of the method of the present invention, the succinicacid substituted intermediate represented by Formula III is converted toa succinic anhydride substituted intermediate represented by Formula IV.The conversion is typically conducted in the presence of a Brønsted acid(or protonic acid), such as a sulfonic acid, and under appropriateconditions, such as with reflux, as represented in the following Scheme2.

With reference to Scheme-2, the Brønsted acid (represented by H⁺) istypically a strong acid, such as a sulfonic acid (e.g., dodecyl benzenesulfonic acid, DBSA). With some embodiments, a heterogeneous catalystcan be used in the reaction represented by Scheme-2. Examples ofheterogeneous catalysts include, but are not limited to, sulfonic acidfunctional perhalogenated olefins, such as sulfonic acid functionalpolytetrafluoroethylene available under the tradename NAFION H availablecommercially from E.I. du Pont de Nemours & Co., Inc. The solvent can beselected from any suitable solvent from which the anhydride product IVcan be separated, such as xylene. The reflux can be conducted underart-recognized conditions, such as described with regard to Scheme-1above. As the reaction/conversion progresses, water is removed from thereaction vessel, and typically collected and measured. Typically, aftercompletion of the reaction, solvent is removed by reduced pressurestripping, leaving crude succinic anhydride substituted intermediaterepresented by Formula IV within the reaction vessel. The crude succinicanhydride substituted intermediate represented by Formula IV can befurther isolated or otherwise purified in accordance with art recognizedmethods, or used in its crude form in the next step of the syntheticsequence.

The succinic anhydride substituted intermediate represented by FormulaIV is next converted to an indanone acid intermediate represented byFormula V, in the next step of the method of the present invention, asrepresented by the following Scheme-3.

The conversion of the succinic anhydride substituted intermediaterepresented by Formula IV to the indanone acid intermediate representedby Formula V, represented by Scheme-3, is typically conducted in thepresence of an acid, such as one or more Lewis acids and/or one or moreBrønsted acids. Examples of acids that can be used in the conversionrepresented by Scheme-3 include, but are not limited to: aluminumchloride (AlCl₃); tin chloride (SnCl₄); Bi(OTf)₃ (bismuthtris-triflate); at least one phosphoric acid, including but not limitedto orthophosphoric acid (H₃PO₄) and/or polyphosphoric acid; andcombinations thereof. With some embodiments of the present invention,the conversion represented by Scheme-3 is performed in the presence of aLewis acid, such as aluminum chloride (AlCl₃). The conversionrepresented by Scheme-3 is typically conducted in the presence of anappropriate solvent, such as a halogenated solvent, from which theindanone acid intermediate V can be separated. Examples of halogenatedsolvents include, but are not limited to halogenated C₁-C₆ alkanes, suchas dichloromethane (DCM). The conversion represented by Scheme-3 is alsotypically conducted under conditions of ambient pressure (e.g.,approximately 1 atm), under an inert atmosphere (e.g., under a nitrogensweep), and an appropriate temperature, such as from −15° C. to 50° C.,or from −10° C. to 40° C., or from 0° C. to 30° C. Conversion of thesuccinic anhydride substituted intermediate represented by Formula IV tothe indanone acid intermediate represented by Formula V, as representedby Scheme-3, is typically referred to an intramolecular Friedel-Craftsreaction.

The conversion represented by Scheme-3 typically results in theformation of a mixture of materials, from which the indanone acidintermediate represented by Formula V is typically isolated. Isolationof the indanone acid intermediate represented by Formula V can beconducted in accordance with art-recognized methods. With someembodiments of the present invention, the indanone acid intermediaterepresented by Formula V is isolated by chromatography, in accordancewith art-recognized methods.

In the next step of the method of the present invention, the indanoneacid intermediate represented by Formula V is reacted with a nucleophilerepresented by Formula VI to form a substituted indanone intermediaterepresented by at least one of Formula VIIa, Formula VIIb and FormulaVIIc, as represented by the following Scheme-4.

As discussed previously herein, M of the nucleophile represented byFormula VI, represents a counterion, and in particular a cation, thatincludes a metal selected from Mg, Li, Cu, and combinations of two ormore thereof. Typically, the counterion M also includes a halogen, andcan be represented by MX⁺. With some embodiments of the presentinvention, the counterion M includes Mg and a halogen, such as Cl (e.g.,MgCl⁺).

With some embodiments of the present invention, the nucleophilerepresented by Formula VI is a Grignard reagent, and the reactionrepresented by Scheme-4 is a Grignard reaction, which is conducted underGrignard reaction conditions. The reaction represented by Scheme-4 istypically conducted in the presence of an appropriate solvent, such astetrahydrofuran (THF), and under conditions of ambient pressure (e.g.,approximately 1 atm), under an inert atmosphere (e.g., under a nitrogensweep), an appropriate temperature, such as from −80° C. to 80° C., orfrom −20° C. to 60° C., or from 0° C. to 20° C., and optionally atelevated temperature, such as under reflux conditions.

With further reference to Scheme-4, the carboxylic acid group of theindanone acid intermediate represented by Formula V typicallydeactivates a molar equivalent of the nucleophile represented by FormulaVI. To address this deactivation, additional nucleophile represented byFormula VI is added to the reaction vessel. With some embodiments, forevery mole of indanone acid intermediate represented by Formula V, twomoles of nucleophile represented by Formula VI are added to or presentwithin the reaction vessel. With further embodiments of the presentinvention, the carboxylic acid group of the indanone acid intermediateis protected, for example converted to an oxazoline group, as will bediscussed in further detail herein.

The substituted indanone intermediate represented by at least one ofFormula VIIa, Formula VIIb and Formula VIIc can be isolated inaccordance with art-recognized methods, or used in a crude form in thenext step of the method of the present invention. The substitutedindanone intermediate represented by at least one of Formula VIIa,Formula VIIb and Formula VIIc is typically isolated and optionallyfurther purified (e.g., by art-recognized column chromatography methods)before the next step of the synthetic method.

The substituted indanone intermediate represented by at least one ofFormula VIIa, Formula VIIb and Formula VIIc is converted to theindeno-fused naphthol represented by Formula I, in the next step of themethod of the present invention. This conversion can be conducted insubstantially one step in the presence of a Brønsted acid, asrepresented by the following Scheme-5.

The conversion/reaction represented by Scheme-5 is typically conductedunder conditions of elevated temperature, for example at a temperaturefrom 20° C. to 200° C., or from 50° C. to 150° C., or from 80° C. to120° C., under conditions of ambient pressure (e.g., approximately 1atm), and under an inert atmosphere, such as a nitrogen sweep. ExamplesOf Brønsted acids that can be used in the conversion represented byScheme-5 include, but are not limited to, carboxylic acids (e.g.,acetic, proponoic, and/or butanoic acid), sulfonic acids (e.g.,R—S(O)(O)—OH, where R is selected from hydrocarbyl or substitutedhydrocarbyl, such as perhalohydrocarbyl), phosphoric acids (e.g.,orthophosphoric acid, one or more polyphosphoric acids, and/or relatedcombinations thereof), and combinations thereof. The Brønsted acid canbe present in a catalytic amount, equimolar amount or excess amount,depending in part on the selection of Brønsted acid(s), such as from0.01 to 50 moles, based on total moles of substituted indanoneintermediate represented by at least one of Formulas VIIa, VIIb andVIIc.

With some embodiments of the present invention, conversion of thesubstituted indanone intermediate represented by at least one of FormulaVIIa, Formula VIIb and Formula VIIc to the indeno-fused naphtholrepresented by Formula I, is conducted in two steps. Initially anindeno-fused naphtho-intermediate represented by Formula X is formed,which is then reacted with a Brønsted acid so as to form theindeno-fused naphthol represented by Formula I, as represented by thefollowing Scheme-6.

With reference to Scheme-6, the R¹⁴ group of the indeno-fusednaphtho-intermediate represented by Formula X is selected from —C(O)—R¹⁵and —S(O)(O)R¹⁵, where R¹⁵ in each case is independently selected fromhydrocarbyl (e.g., C₁-C₁₀ alkyl) and halohydrocarbyl (e.g., C₁-C₁₀perhaloalkyl).

The initial conversion or reaction of step-(a) of Scheme-6, is typicallyconducted in the presence of a material selected from carboxylic acidhalide, carboxylic acid anhydride, sulfonyl halide, sulfonyl anhydrideand combinations thereof. The carboxylic acid halide, carboxylic acidanhydride and/or sulfonyl halide is typically present in at least anequimolar amount relative to the substituted indanone intermediaterepresented by at least one of Formulas VIIa, VIIb and VIIc. Carboxylicacid halides that can be used in step-(a), can be represented by thestructure, R^(c)—C(O)—X, where R^(c) is selected from hydrocarbyl orsubstituted hydrocarbyl, and X is selected from halogen (e.g., Cl).Sulfonyl halides that can be used in step-(a), can be represented by thestructure, R^(c)—S(O)(O)—X, where R^(c) is selected from hydrocarbyl orsubstituted hydrocarbyl, and X is selected from halogen (e.g., Cl).Sulfonyl anhydrides that can be used in step-(a), can be represented bythe structure, R^(d)—S(O₂)—O—(O₂)S—R^(e) where R^(d) and R^(e) are eachindependently selected from hydrogen, hydrocarbyl, and substitutedhydrocarbyl (e.g., halohydrocarbyl, such as C₁-C₁₀ perhaloalkyl, e.g.,—CF₃). Carboxylic acid anhydrides that can be used in step-(a), can berepresented by the structure, R^(d)—C(O)—O—C(O)—R^(e), where R^(d) andR^(e) are each independently selected from hydrogen, hydrocarbyl, andsubstituted hydrocarbyl (e.g., halohydrocarbyl, such as C₁-C₁₀perhaloalkyl, e.g., —CF₃).

The initial conversion or cyclization reaction of step-(a) of Scheme-6,can alternatively be conducted in the presence of a suitable catalyst.With some embodiments of the present invention, step-(a) of Scheme-6 isconducted in the presence of a catalytic amount of Bi(SO₃CF₃)₃, whichcan be present in an amount of from 0.01 to 0.01 moles, based on totalmoles of substituted indanone intermediate represented by at least oneof Formulas VIIa, VIIb, and VIIc.

The indeno-fused naphtho-intermediate represented by Formula X isconverted to the indeno-fused naphthol represented by Formula I instep-(b) of Scheme-6 in the presence of a Brønsted acid. The Brønstedacid can be selected from hydrogen halides (HX, where X is halogen) suchas HCl, and/or carboxylic acids. The Brønsted acid is typically presentin an excess amount relative to the amount of indeno-fusednaphtho-intermediate represented by Formula X. For example theconversion of step-(b) can be conducted in the presence of concentratedhydrogen halide acid, such as concentrated HCl. The conversion ofstep-(b) is typically conducted in the presence of a solvent, such asmethanol, under conditions of elevated temperature, for example at atemperature from 20° C. to 200° C., or from 50° C. to 150° C., or from80° C. to 120° C., under conditions of ambient pressure (e.g.,approximately 1 atm), and under an inert atmosphere, such as a nitrogensweep.

Depending on the ring-position, identity and number of the R² group(s)of the substituted indanone intermediate represented by at least one ofFormulas VIIa, VIIb and VIIc, a mixture of indeno-fused naphtholsrepresented by Formula I can be obtained in the method of the presentinvention. One or more of the structural isomers of the mixture ofindeno-fused naphthols can be isolated in accordance with art-recognizedmethods, such as chromatographic methods. Alternatively, the mixture ofindeno-fused naphthols can be left unresolved.

For purposes of illustration, when R^(g) and R^(h) are each methyl(—CH³), m is zero, n is 1, and R² is a methoxy group (—OCH₃) located atposition-3 of the ring of the substituted indanone intermediaterepresented by at least one of Formulas VIIa, VIIb and VIIc, the methodof the present invention can result in the formation of two structuralisomers of the indeno-fused naphthol, as represented by the followingFormulas Ia and Ib.

The indeno-fused naphthols represented by Formulas Ia and Ib can bepresent in a wide range of relative amounts. For example theindeno-fused naphthol represented by Formula Ia can be present in anamount of from 1 to 99 mole percent, or from 20 to 80 mole percent, orfrom 30 to 70 mole percent, and the indeno-fused naphthol represented byFormula Ib can be present in an amount of from 1 to 99 mole percent, orfrom 20 to 80 mole percent, or from 30 to 70 mole percent, based in eachcase on total moles of indeno-fused naphthol represented by Formula Iaand Ib. With some embodiments, the indeno-fused naphthol represented byFormula Ia can be present in an amount of from 15 to 35 mole percent(e.g., about 30 mole percent), and the indeno-fused naphthol representedby Formula Ib can be present in an amount of from 65 to 85 mole percent(e.g., about 70 mole percent), in each case based on total moles ofindeno-fused naphthol represented by Formula Ia and Ib.

The method of the present invention can result in the formation ofindeno-fused naphthols represented by Formula I in a wide range ofyields. For example the method of the present invention can result inthe formation of indeno-fused naphthols represented by Formula I yieldsof from 1 to 85 mole percent, based on theoretical moles of indeno-fusednaphthol that could be produced. Typically, the method of the presentinvention results in the formation of indeno-fused naphthols in yieldsof at least 50 mole percent, such as from 50 to 85 mole percent, or from60 to 75 mole percent, based on theoretical moles of indeno-fusednaphthol that could be produced.

With some embodiments of the present invention, the carboxylic acidgroup of the indanone acid intermediate represented by Formula V, can beprotected so as to minimize or prevent reaction between the protectedcarboxylic acid group and the nucleophile represented by Formula VI.With some embodiments, the indanone acid intermediate represented byFormula V is converted to an indanone oxazoline intermediate representedby the following Formula VIII.

With reference to the indanone oxazoline intermediate represented byFormula VIII, m, R¹, R^(g), and R^(h) are in each ease independentlyselected from those values, ranges, and groups as described above andfurther herein with reference to Formula I, or in each caseindependently represent one or more precursors of those groups asdescribed above and further herein with reference to Formula I. Withfurther reference to Formula VIII, R⁴ and R⁵ are each independentlyselected from hydrogen, hydrocarbyl and substituted hydrocarbyl.

The indanone oxazoline intermediate represented by Formula VIII can beformed by suitable methods. With some embodiments, the indanoneoxazoline intermediate represented by Formula VIII can be formed byreaction of the indanone acid intermediate represented by Formula V withan amino alcohol, such as 2-amino-2-methyl-3-hydroxy propane, asrepresented by the following Scheme-7.

The reaction depicted in Scheme-7 is typically conducted in the presenceof a suitable solvent, such as xylene, and under appropriate refluxconditions.

The indanone oxazoline intermediate represented by Formula VIII canalternatively be formed by a multi-step synthetic scheme that involvesthe formation of a carboxylic acid halide intermediate, as representedby the following Scheme-8.

In step-(a) of Scheme-8, thionyl chloride (SOCl₂) is reacted with theindanone acid intermediate represented by Formula V under art-recognizedconditions, which results in formation of an indanone acid chlorideintermediate represented by Formula V-1. The indanone acid chlorideintermediate represented by Formula V-1 is then reacted in step-(b) withan amino alcohol, such as 2-amino-2-methyl-3-hydroxy propane, whichresults in the formation of the indanone hydroxyl functional amideintermediate represented by Formula V-2. In step-(c), the indanonehydroxyl functional amide intermediate represented by Formula V-2 iscyclized to form the indanone oxazoline intermediate represented byFormula VIII in the presence of thionyl chloride and base, such assodium hydroxide.

The indanone oxazoline intermediate represented by Formula VIII isreacted with the nucleophile represented by Formula VI, so as to form asubstituted indanone oxazoline intermediate represented by at least oneof the following Formulas IXa and IXb.

The reaction of the indanone oxazoline intermediate represented byFormula VIII with the nucleophile represented by Formula VI, so as toform the substituted indanone oxazoline intermediate represented by atleast one of Formulas IXa and IXb, can be conducted in accordance withthe description provided previously herein with regard to Scheme-4.Typically, however, an excess of the nucleophile represented by FormulaVI, is not required when reacted with the indanone oxazolineintermediate represented by Formula VIII. With some embodiments, asubstantially equimolar amount of nucleophile represented by Formula VIis reacted with the indanone oxazoline intermediate represented byFormula VIII.

The substituted indanone oxazoline intermediate represented by at leastone of Formulas IXa and IXb is then converted to the substitutedindanone intermediate represented by at least one of Formulas VIIa, VIIband VIIc. More particularly, the oxazoline group is removed from thesubstituted indanone oxazoline intermediate represented by at least oneof Formulas IXa and IXb, thus resulting in formation of the substitutedindanone intermediate represented by at least one of Formulas VIIa, VIIband VIIc, as represented by the following Scheme-9.

With reference to Scheme-9, removal of the oxazoline group is typicallyconducted in the presence of a Brønsted acid, and in particular aninorganic acid, such as concentrated HCl, and under appropriate refluxconditions. Appropriate work-up of the resulting substituted indanoneintermediate represented by at least one of Formulas VIIa, VIIb and VIIcis typically conducted, for example to remove the amino alcohol and/orsalt thereof.

After removal of the oxazoline group as represented in Scheme-9, andappropriate work-up, the substituted indanone intermediate representedby at least one of Formulas VIIa, VIIb and VIIc is then converted to theindeno-fused naphthol represented by Formula I, in accordance with thedescription provided previously herein.

The indeno-fused naphthols prepared by the method of the presentinvention can be used in numerous applications, such as additives incompositions, or as intermediates in the synthesis of additionalcompounds, such as non-photochromic (or static) dyes and photochromicdyes. Embodiments of the present invention also include a method ofmaking an indeno-fused naphthopyran represented by Formula XI, whichinvolves forming the indeno-fused naphthol represented by Formula I, asdescribed previously herein, and then reacting the indeno-fused naphtholwith a propargyl alcohol represented by Formula XII. Reaction of theindeno-fused naphthol represented by Formula I and the propargyl alcoholrepresented by Formula XII can be represented by the followingScheme-10.

With reference to Scheme-10, the indeno-fused naphthol represented byFormula I is reacted or coupled with the propargyl alcohol representedby Formula XII in the presence of a catalytic amount of a Brønsted acid,such as dodecyl benzene sulfonic acid (DDBSA) or para-toluene sulfonicacid (pTSA), in a suitable solvent, such as a haloalkane (e.g.,trichloromethane), under an inert atmosphere (e.g., a nitrogen sweep),and at an appropriate temperature, for example, from 0° C. to 150° C.,or from 10° C. to 100° C., or from 20° C. to 80° C.

The groups and substituents of the indeno-fused naphthol represented byFormula I, the indeno-fused naphthopyran represented by Formula XI, andthe compounds and intermediates used in their preparation, are describedin further detail as follows. With some embodiments of the presentinvention, R¹ for each m, and R² for each n, are in each caseindependently selected from: a reactive substituent; a compatiblizingsubstituent; hydrogen; fluoro; chloro; C₁-C₆ alkyl; C₃-C₇ cycloalkyl;substituted or unsubstituted phenyl; —OR₁₀′ or —OC(═O)R₁₀′, wherein R₁₀′is hydrogen, C₁-C₆ alkyl, phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkylsubstituted phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxy substitutedphenyl(C₁-C₃)alkyl, (C₁-C₆)alkoxy(C₂-C₄)alkyl, C₃-C₇ cycloalkyl, ormono(C₁-C₄)alkyl substituted C₃-C₇ cycloalkyl. The phenyl substituents(i.e., the substituents of the substituted phenyl) may be selected fromhydroxyl, halogen, carbonyl, C₁-C₆ alkoxycarbonyl, cyano,halo(C₁-C₆)alkyl, C₁-C₆ alkyl or C₁-C₆ alkoxy.

Alternatively or in addition to the previously recited classes andexamples, R¹ for each m, and R² for each n, are in each caseindependently selected from: —N(R₁₁′)R₁₂′, wherein R₁₁′ and R₁₂′ areeach independently hydrogen, C₁-C₈ alkyl, phenyl, naphthyl, furanyl,benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl,fluorenyl, C₁-C₈ alkylaryl, C₃-C₂₀ cycloalkyl, C₄-C₂₀ bicycloalkyl,C₅-C₂₀ tricycloalkyl or C₁-C₈ alkoxyalkyl, wherein the aryl group isphenyl or naphthyl, or R₁₁′ and R₁₂′ come together with the nitrogenatom to form a C₃-C₂₀ hetero-bicycloalkyl ring or a C₄-C₂₀hetero-tricycloalkyl ring.

Further alternatively or in addition to the previously recited classesand examples, R¹ for each m, and R² for each n, can in each case beindependently selected from, a nitrogen containing ring substituentrepresented by the following general (or graphic) formula XIIIA:

With the nitrogen ring substituent represented by general formula XIIIA,each —Y— is independently chosen for each occurrence from —CH₂—,—CH(R₁₃′)—, —C(R₁₃′)₂—, —CH(aryl)-, —C(aryl)₂-, and —C(R₁₃′)(aryl)-, andZ is —Y—, —S—, —S(O)—, —SO₂—, —NH—, —N(R₁₃′)—, or —N(aryl)-, whereineach R₁₃′ is independently C₁-C₆ alkyl, each aryl is independentlyphenyl or naphthyl, in is an integer 1, 2 or 3, and p is an integer 0,1, 2, or 3, provided that when p is 0, Z is —Y—.

Additionally or alternatively, R¹ for each m, and R² for each n, can ineach case also be independently selected from a nitrogen containing ringsubstituent represented by general formula XIIIB and/or general formulaXIIIC:

For the nitrogen containing ring substituents represented by generalformulas XIIIB and XIIIC, R₁₅, R₁₆, and R₁₇ are each independentlyselected from hydrogen, C₁-C₆ alkyl, phenyl, or naphthyl, or the groupsR₁₅ and R₁₆ together form a ring of 5 to 8 carbon atoms and each R^(d)is independently for each occurrence selected from C₁-C₆ alkyl, C₁-C₆alkoxy, fluoro or chloro, and Q is an integer 0, 1, 2, or 3.

Further alternatively or additionally, R¹ for each m, and R² for each n,can in each case also be independently selected from unsubstituted,mono-, or di-substituted C₄-C₁₈ spirobicyclic amine, or unsubstituted,mono-, and di-substituted C₄-C₁₈ spirotricyclic amine. The substituentsof the spirobicyclic amines and the spirotricyclic amines may in eachcase be independently selected from aryl, C₁-C₆ alkyl, C₁-C₆ alkoxy, orphenyl(C₁-C₆)alkyl.

With some embodiments of the present invention, two adjacent R¹ groups,and/or two adjacent R² groups, can together form a group represented bythe following general formula XIIID or general formula XIIIE,

With the groups represented by general formulas XIIID and XIIIE, T andT′ are each independently oxygen or the group —NR₁₁—, where R₁₁, R₁₅,and R₁₆ are each as set forth and described previously herein.

The R^(g) and R^(h) groups with some embodiments of the presentinvention, can each be independently selected from: a reactivesubstituent; a compatiblizing substituent; hydrogen; hydroxy; C₁-C₆alkyl; hydroxy(C₁-C₆)alkyl; C₃-C₇ cycloalkyl; allyl; substituted orunsubstituted phenyl; substituted or unsubstituted benzyl; chloro;fluoro; the group —C(═O)W′, wherein W′ is hydrogen, hydroxy, C₁-C₆alkyl, C₁-C₆ alkoxy, the unsubstituted, mono-or di-substituted arylgroups phenyl or naphthyl-, phenoxy, mono- or di-(C₁-C₆)alkoxysubstituted phenoxy, mono- or di-(C₁-C₆)alkoxy substituted phenoxy,amino, mono(C_(j)—C₆)alkylamino, di(C₁-C₆)alkylamino, phenylamino, mono-or di-(C₁-C₆)alkyl substituted phenylamino, or mono- or di-(C₁-C₆)alkoxysubstituted phenylamino. The phenyl, benzyl, or aryl group substituents(e.g., the substituents of the substituted phenyl, substituted benzyland substituted aryl groups) are each independently selected from C₁-C₆alkyl or C₁-C₆ alkoxy.

The R^(g) and R^(h) groups with some embodiments of the presentinvention, can also each be independently selected from anunsubstituted, mono- di- or tri-substituted group chosen from phenyl,naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl,thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl orindolyl; each of said group substituents in (ii) being chosenindependently for each occurrence from chloro, fluoro, C₁-C₆ alkyl orC₁-C₆ alkoxy.

The R^(g) and R^(h) groups can also, with some embodiments of thepresent invention, each be independently selected from amono-substituted phenyl, in which the phenyl has a substituent locatedat the para position thereof, which is a linking group, —(CH₂)_(t)— or—O—(CH₂)_(t)—, that is connected to an aryl group which is a member of a(or another) photochromic material, such as a naphthopyran orbenzopyran, and t is chosen from the integer 1, 2, 3, 4, 5 or 6.

Alternatively, the R^(g) and R^(h) groups can each be independentlyselected from —CH(R¹⁰)G, where the R¹⁰ group is chosen from hydrogen,C₁-C₆ alkyl or an unsubstituted, Mono- or di-substituted aryl group,such as phenyl or naphthyl, and G is chosen, from —CH₂OR¹¹, where R¹¹ ischosen from hydrogen, —C(O)R¹⁰, C₁-C₆ alkyl, C₁-C₃ alkoxy(C₁-C₆)alkyl,phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxy substituted phenyl(C₁-C₃)alkyl, oran unsubstituted, mono- or di-substituted aryl group, such as phenyl ornaphthyl, each of the aryl group substituents (e.g., of the phenyl andnaphthyl, group substituents) being independently chosen from C₁-C₆alkyl or C₁-C₆ alkoxy.

Further alternatively, with some embodiments: of the present invention,R^(g) and R^(h) together form a spiro substituent selected from asubstituted or unsubstituted spiro-carbocyclic ring containing 3 to 6carbon atoms, a substituted or unsubstituted spiro-heterocyclic ringcontaining 1 or 2 oxygen atoms and 3 to 6 carbon atoms including thespirocarbon atom, said spiro-carbocyclic ring and spiro-heterocyclicring being annellated with 0, 1 or 2 benzene rings. The substituents ofthe recited classes of spiro substituents can be selected from, forexample, hydrogen or C₁-C₂₀ alkyl.

With some embodiments of the present invention, R¹ for each m, and R²for each n, are in each case independently selected from unsubstitutedphenyl, substituted phenyl, C₁-C₆ alkyl, C₃-C₇ cycloalkyl, C₁-C₈haloalkyl, fluoro, chloro, and —O—R₁₀′. With further embodiments of thepresent invention, R³ is selected from hydrogen, C₁-C₈ alkyl, C₁-C₈haloalkyl, and C₃-C₇ cycloalkyl.

The B and B′ groups of the indeno-fused naphthopyran represented byFormula XI, and/or the propargyl alcohol represented by Formula XII caneach independently be selected from unsubstituted aryl, substitutedaryl, unsubstituted heteroaryl, substituted heteroaryl, polyalkoxy, andpolyalkoxy having a polymerizable group. Alternatively, B and B′ takentogether can form a ring structure selected from unsubstitutedfluoren-9-ylidene, substituted fluoren-9-ylidene, saturatedspiro-monocyclic hydrocarbon ring, saturated spiro-bicyclic hydrocarbonring, and spiro-tricyclic hydrocarbon ring.

More particularly, B and B′ can each independently be selected from: anaryl group that: is mono-substituted with a reactive substituent or acompatiblizing substituent; a substituted phenyl; a substituted aryl; asubstituted 9-julolindinyl; a substituted heteroaromatic group chosenfrom pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl,carbazoyl, benzopyridyl, indolinyl, and fluorenyl, wherein the phenyl,aryl, 9-julolindinyl, or heteroaromatic substituent is the reactivesubstituent R; an unsubstituted, mono-, di-, or tri-substituted phenylor aryl group; 9-julolidinyl; or an unsubstituted, mono- ordi-substituted heteroaromatic group chosen from pyridyl, furanyl,benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl,benzopyridyl, indolinyl, and fluorenyl.

The phenyl, aryl and heteroaromatic substituents (i.e., the substituentsof the substituted phenyl, aryl and heteroaromatic groups) of the B andB′ groups may each be independently selected from: hydroxyl, a group—C(═O)R₂₁, wherein R₂₁ is OR₂₂, —N(R₂₃)R₂₄, piperidino, or morpholino,wherein R₂₂ is allyl, C₁-C₆ alkyl, phenyl, mono(C₁-C₆)alkyl substitutedphenyl, mono(C₁-C₆)alkoxy substituted phenyl, phenyl(C₁-C₃)alkyl,mono(C₁-C₆)alkyl substituted phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxysubstituted phenyl(C₁-C₃)alkyl, C₁-C₆ alkoxy(C₂-C₄)alkyl or C₁-C₆haloalkyl, R₂₃ and R₂₄ are each independently C₁-C₆ alkyl, C₅-C₇cycloalkyl, phenyl or substituted phenyl, the phenyl substituents beingC₁-C₆ alkyl or C₁-C₆ alkoxy, and said halo substituent is chloro orfluoro, aryl, mono(C₁-C₁₂)alkoxyaryl, di(C₁-C₁₂)alkoxyaryl,mono(C₁-C₁₂)alkylaryl, di(C₁-C₁₂)alkylaryl, haloaryl, C₃-C₇cycloalkylaryl, C₃-C₇ cycloalkyl, C₃-C₇ cycloalkyloxy, C₃-C₇cycloalkyloxy(C₁-C₁₂)alkyl, C₃-C₇ cycloalkyloxy(C₁-C₁₂)alkoxy,aryl(C₁-C₁₂)alkyl, aryl(C₁-C₁₂)alkoxy, aryloxy, aryloxy(C₁-C₁₂)alkyl,aryloxy(C₁-C₁₂)alkoxy, mono- or di(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkyl, mono-or di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkyl, mono- ordi-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkoxy, mono- ordi-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkoxy, amino, mono- ordi-(C₁-C₁₂)alkylamino, diarylamino, piperazino,N—(C₁-C₁₂)alkylpiperazino, N-arylpiperazino, aziridino, indolino,piperidino, morpholino, thiomorpholino, tetrahydroquinolino,tetrahydroisoquinolino, pyrrolidyl, alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂alkoxy, mono(C₁-C₁₂)alkoxy(C₁-C₁₂)alkyl, acryloxy, methacryloxy, orhalogen.

The B and B′ groups can also each independently be an unsubstituted ormono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl,imidazolinyl, pyrrolinyl, phenothiazinyl, phenoxazinyl, phenazinyl, andacridinyl. The substituents of these mono-substituted groups are eachindependently selected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, phenyl, orhalogen.

In addition, the B and B′ groups may each be independently selected froma group represented by the following general formulas XIVA or XIVB,

Independently with each of general formulas XIVA and XIVB, K is —CH₂— or—O—, and Φ is —O— or substituted nitrogen, provided that when Φ issubstituted nitrogen, K is —CH₂—. The substituted nitrogen substituentsare hydrogen, C₁-C₁₂ alkyl, or C₁-C₁₂ acyl. Each R₂₅ is independentlyselected for each occurrence from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, hydroxy,and halogen, and each u is independently an integer ranging from 0 to 2.The R₂₆ and R₂₇ groups are each independently hydrogen or C₁-C₁₂ alkyl.

Each B and B′ group can independently be a group represented by thefollowing general formula XV,

With the group represented by general formula XV, R₂₈ is hydrogen orC₁-C₁₂ alkyl, and R₂₉ is an unsubstituted, mono- or di-substituted groupchosen from naphthyl, phenyl, furanyl, and thienyl. The substitutents ofthe mono- or di-substituted naphthyls, phenyls, furanyls, and thienyls,are in each case independently selected from C₁-C₁₂ alkyl, C₁-C₁₂alkoxy, or halogen.

The B and B′ groups can together form a member selected from, afluoren-9-ylidene, a mono-substituted fluoren-9-ylidene, or adi-substituted fluoren-9-ylidene. The substituents of themono-substituted fluoren-9-ylidene, and the di-substitutedfluoren-9-ylidene can in each case be independently selected from C₁-C₁₂alkyl, C₁-C₁₂ alkoxy, or halogen.

With some embodiments of the present invention, B and B′ are eachindependently selected from aryl substituted with C₁-C₆ alkoxy, and aryl(e.g., phenyl) substituted with morpholino.

With some embodiments of the present invention, B and B′ can each beindependently selected from polyalkoxy, and polyalkoxy having apolymerizable group. The polyalkoxy, and polyalkoxy having apolymerizable group from which B and B′ can each be independentlyselected can be represented by the following Formulas XXV and XXVI.

—Z[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]Z′  XXV

—[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]Z′  XXVI

With Formulas XXV and XXVI, —Z is chosen from —C(O)— or —CH₂—, Z′ ischosen from C₁-C₃ alkoxy or a polymerizable group. As used herein and inthe claims, the term “polymerizable group” means any functional groupcapable of participating in a polymerization reaction.

With some embodiments, polymerization of the polymerizable indeno-fusednaphthopyrans can occur by mechanisms described with regard to thedefinition of “polymerization” in Hawley's Condensed ChemicalDictionary, Thirteenth Edition, 1997, John Wiley & Sons, pages 901-902.Those mechanisms include: by “addition,” in which free radicals are theinitiating agents that react with the ethylenically unsaturated doublebond of the monomer by adding to it on one side at the same timeproducing a new free electron on the other side; by “condensation,”involving the splitting out of a component, such as water molecules, bytwo reacting monomers; and by so-called “oxidative coupling.”

Examples of polymerizable groups include, but are not limited to,hydroxy, thiol, isocyanate groups, oxirane groups (e.g.,oxiranylmethyl), radically polymerizable ethylenically unsaturatedgroups, allyl groups, (meth)acryloxy, and 2-(methacryloxy)ethylcarbamyl.When there are 2 or more polymerizable groups on the naphthopyran, theymay be the same or different.

With some embodiments and with further reference to Formulas XXV andXXVI: the group, —(OC₂H₄)_(x)—, can represent poly(ethylene oxide); thegroup —(OC₃H₆)_(y)—, can represent poly(propylene oxide); and the group—(OC₄H₈)_(z)—, can represent poly(butylene oxide). When used incombination, the poly(ethylene oxide), poly(propylene oxide) andpoly(butylene oxide) groups of Formulas XXV and XXVI can be in a randomor block order within the polyalkoxy moiety. The subscript letters x, yand z of Formulas XXV and XXVI are each independently a number between 0and 50, and the sum of x, y and z is between 2 and 50. The sum of x, yand z can be any number that falls within the range of 2 to 50 (e.g., 2,3, 4 . . . 50). This sum can also range from any lower number to anyhigher number within the range of 2 to 50 (e.g., 6 to 50, 31 to 50). Thenumbers for x, y, and z are average values and can be partial numbers(e.g., 9.5).

As previously discussed, each of the R¹, R², R³, B and B′ groups canindependently be selected from or include at least one of a reactivesubstituent and/or a compatiblizing substituent. If the variouscompounds and/or intermediates described previously herein, such as theindeno-fused naphthol represented by Formula I, and/or the indeno-fusednaphthopyran represented by Formula XI, include multiple reactivesubstituents and/or multiple compatiblizing substituents, each reactivesubstituent and each compatiblizing substituent can be independentlychosen.

The reactive substituent and the compatibilizing substituent can eachindependently be represented in each case by one of:

-A′-D-E-G-J (XVI); -G-E-G-J (XIX); -D-E-G-J (XXII); -A′-D-J (XVII);-D-G-J (XX); -D-J (XXIII); -A′-G-J (XVIII); -G-J (XXI); and -A′-J(XXIV).

With formulas (XVI) through (XXIV), non-limiting examples of groups that-A′- can represent according to various non-limiting embodimentsdisclosed herein include —O—, —C(═O)—, —CH₂—, —OC(═O)— and —NHC(═O)—,provided that if -A′- represents —O—, -A′- forms at least one bond with-J.

Non-limiting examples of groups that -D- can represent according tovarious non-limiting embodiments include a diamine residue or aderivative thereof, wherein a first amino nitrogen of said diamineresidue can form a bond with -A′-, or a substituent or an availableposition on the compound (such as the indeno-fused naphthol orindeno-fused naphthopyran), and a second amino nitrogen of said diamineresidue can form a bond with -E-, -G- or -J; and an amino alcoholresidue or a derivative thereof, wherein an amino nitrogen of the aminoalcohol residue can form a bond with -A′-, or a substituent or anavailable position on the compound (such as the indeno-fused naphthol orindeno-fused naphthopyran), and an alcohol oxygen of said amino alcoholresidue can form a bond with -E-, -G- or -J. Alternatively, according tovarious non-limiting embodiments disclosed herein the amino nitrogen ofsaid amino alcohol residue can form a bond with -E-, -G- or -J, and saidalcohol oxygen of said amino alcohol residue may form a bond with -A′-,or a substituent or an available position on the compound (such as theindeno-fused naphthol or indeno-fused naphthopyran).

Non-limiting examples of suitable diamine residues that -D- canrepresent include an aliphatic diamine residue, a cyclo aliphaticdiamine residue, a diazacycloalkane residue, an azacyclo aliphatic amineresidue, a diazacrown ether residue, and an aromatic diamine residue.Specific non-limiting examples diamine residues that can be used inconjunction with various non-limiting embodiments disclosed hereininclude the following:

Non-limiting examples of suitable amino alcohol residues that -D- mayrepresent include an aliphatic amino alcohol residue, a cyclo aliphaticamino alcohol residue, an azacyclo aliphatic alcohol residue, adiazacyclo aliphatic alcohol residue and an aromatic amino alcoholresidue. Specific non-limiting examples amino alcohol residues that maybe used in conjunction with various non-limiting embodiments disclosedherein include the following:

With continued reference to formulas (XVI) through (XXIV) above,according to various non-limiting embodiments disclosed herein, -E- canrepresent a dicarboxylic acid residue or a derivative thereof, wherein afirst carbonyl group of said dicarboxylic acid residue may form a bondwith -G- or -D-, and a second carbonyl group of said dicarboxylic acidresidue may form a bond with -G-. Non-limiting examples of suitabledicarboxylic acid residues that -E- can represent include an aliphaticdicarboxylic acid residue, a cycloaliphatic dicarboxylic acid residueand an aromatic dicarboxylic acid residue. Specific non-limitingexamples of dicarboxylic acid residues that can be used in conjunctionwith various non-limiting embodiments disclosed herein include thefollowing:

According to various non-limiting embodiments disclosed herein, -G- canrepresent a group —[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]—O—, wherein x, yand z are each independently chosen and range from 0 to 50, and a sum ofx, y, and z ranges from 1 to 50; a polyol residue or a derivativethereof, wherein a first polyol oxygen of said polyol residue may form abond with -A′-, -D-, -E-, or a substituent or an available position onthe indeno-fused naphthopyran, and a second polyol oxygen of said polyolmay form a bond with -E- or -J; or a combination thereof, wherein thefirst polyol oxygen of the polyol residue forms a bond with a group-[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]— to form the group—[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]—O—), and the second polyol oxygenforms a bond with -E- or -J. Non-limiting examples of suitable polyolresidues that -G- can represent include an aliphatic polyol residue, acyclo aliphatic polyol residue and an aromatic polyol residue.

More particular, illustrative and non-limiting examples of polyols fromwhich the polyol residues that -G- can represent can be formed accordingto various non-limiting embodiments disclosed herein include: (a) lowmolecular weight polyols having an average molecular weight less than500, such as, but not limited to, those set forth in U.S. Pat. No.6,555,028 at col. 4, lines 48-50, and col. 4, line 55 to col. 6, line 5,which disclosure is hereby specifically incorporated by referenceherein; (b) polyester polyols, such as, but not limited to, those setforth in U.S. Pat. No. 6,555,028 at col. 5, lines 7-33, which disclosureis hereby specifically incorporated by reference herein; (c) polyetherpolyols, such as but not limited to those set forth in U.S. Pat. No.6,555,028 at col. 5, lines 34-50, which disclosure is herebyspecifically incorporated by reference herein; (d) amide-containingpolyols, such as, but not limited to, those set forth in U.S. Pat. No.6,555,028 at col. 5, lines 51-62, which disclosure is herebyspecifically incorporated by reference; (e) epoxy polyols, such as, butnot limited to, those set forth in U.S. Pat. No. 6,555,028 at col. 5line 63 to col. 6, line 3, which disclosure is hereby specificallyincorporated by reference herein; (f) polyhydric polyvinyl alcohols,such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028at col. 6, lines 4-12, which disclosure is hereby specificallyincorporated by reference herein; (g) urethane polyols, such as, but notlimited to those set forth in U.S. Pat. No. 6,555,028 at col. 6, lines13-43, which disclosure is hereby specifically incorporated by referenceherein; (h) polyacrylic polyols, such as, but not limited to those setforth in U.S. Pat. No. 6,555,028 at col. 6, lines 43 to col. 7, line 40,which disclosure is hereby specifically incorporated by referenceherein; (i) polycarbonate polyols, such as, but not limited to, thoseset forth in U.S. Pat. No. 6,555,028 at col. 7, lines 41-55, whichdisclosure is hereby specifically incorporated by reference herein; and(j) mixtures of such polyols.

With further reference to formulas (XVI) through (XXIV), according tovarious non-limiting embodiments disclosed herein, -J can represent agroup —K, wherein —K represents a group such as, but not limited to,—CH₂COOH, —CH(CH₃)COOH, —C(O)(CH₂)_(w)COOH, —C₆H₄SO₃H, —C₅H₁₀SO₃H,—C₄H₈SO₃H, —C₃H₆SO₃H, —C₂H₄SO₃H and —SO₃H, wherein “w” ranges from 1 to18. According to other non-limiting embodiments -J can representhydrogen that forms a bond with an oxygen or a nitrogen of linking groupto form a reactive moiety such as —OH or —NH. For example, according tovarious non-limiting embodiments disclosed herein, -J can representhydrogen, provided that if -J represents hydrogen, -J is bonded to anoxygen of -D- or -G-, or a nitrogen of -D-.

According to still further non-limiting embodiments, -J can represent agroup -L or residue thereof, wherein -L can represent a reactive moiety.For example, according to various non-limiting embodiments disclosedherein -L can represent a group such as, but not limited to, acryl,methacryl, crotyl, 2-(methacryloxy)ethylcarbamyl,2-(methacryloxy)ethoxycarbonyl, 4-vinylphenyl, vinyl, 1-chlorovinyl orepoxy. As used herein, the terms acryl, methacryl, crotyl,2-(methacryloxy)ethylcarbamyl, 2-(methacryloxy)ethoxycarbonyl,4-vinylphenyl, vinyl, 1-chlorovinyl, and epoxy refer to the followingstructures:

As previously discussed, -G- can represent a residue of a polyol, whichis defined herein to include hydroxy-containing carbohydrates, such asthose set forth in U.S. Pat. No. 6,555,028 at col. 7, line 56 to col. 8,line 17, which disclosure is hereby specifically incorporated byreference herein. The polyol residue can be formed, for example andwithout limitation herein, by the reaction of one or more of the polyolhydroxyl groups with a precursor of -A′-, such as a carboxylic acid or amethylene halide, a precursor of polyalkoxylated group, such aspolyalkylene glycol, or a hydroxyl substituent of the indeno-fusednaphthopyran. The polyol can be represented by q-(OH)_(a) and theresidue of the polyol can be represented by the formula —O-q-(OH)_(a-1),wherein q is the backbone or main chain of the polyhydroxy compound and“a” is at least 2.

Further, as discussed above, one or more of the polyol oxygens of -G-can form a bond with -J (i.e., forming the group -G-J). For example,although not limiting herein, wherein the reactive and/or compatiblizingsubstituent comprises the group -G-J, if -G- represents a polyol residueand -J represents a group —K that contains a carboxyl terminating group,-G-J can be produced by reacting one or more polyol hydroxyl groups toform the group —K (for example as discussed with respect to Reactions Band C at col. 13, line 22 to col. 16, line 15 of U.S. Pat. No.6,555,028, which disclosure is hereby specifically incorporated byreference herein) to produce a carboxylated polyol residue.Alternatively, if -J represents a group —K that contains a sulfo orsulfono terminating group, although not limiting herein, -G-J can beproduced by acidic condensation of one or more of the polyol hydroxylgroups with HOC₆H₄SO₃H; HOC₅H₁₀SO₃H; HOC₄H₈SO₃H; HOC₃H₆SO₃H; HOC₂H₄SO₃H;or H₂SO₄, respectively. Further, although not limiting herein, if -G-represents a polyol residue and -J represents a group -L chosen fromacryl, methacryl, 2-(methacryloxy)ethylcarbamyl and epoxy, -L can beadded by condensation of the polyol residue with acryloyl chloride,methacryloyl chloride, 2-isocyanatoethyl methacrylate orepichlorohydrin, respectively.

The indeno-fused naphthopyrans prepared by the method of the presentinvention, can be used to render compositions and/or articlesphotochromic. Examples of articles that can be rendered photochromic bythe indeno-fused naphthopyrans of the present invention include, but arenot limited to, optical elements, displays, windows (or transparencies),mirrors, and components or elements of liquid crystal cells. As usedherein the term “optical” means pertaining to or associated with lightand/or vision. Examples of optical elements that can be renderedphotochromic include, without limitation, ophthalmic elements, displayelements, windows, mirrors, and liquid crystal cell elements. As usedherein the term “ophthalmic” means pertaining to or associated with theeye and vision. Non-limiting examples of ophthalmic elements includecorrective and non-corrective lenses, including single vision ormulti-vision lenses, which may be either segmented or non-segmentedmulti-vision lenses (such as, but not limited to, bifocal lenses,trifocal lenses and progressive lenses), as well as other elements usedto correct, protect, or enhance (cosmetically or otherwise) vision,including without limitation, magnifying lenses, protective lenses,visors, goggles, as well as, lenses for optical instruments (forexample, cameras and telescopes). As used herein the term “display”means the visible or machine-readable representation of information inwords, numbers, symbols, designs or drawings. Non-limiting examples ofdisplay elements include screens, monitors, and security elements, suchas security marks. As used herein the term “window” means an apertureadapted to permit the transmission of radiation there-through.Non-limiting examples of windows include automotive and aircrafttransparencies, windshields, filters, shutters, and optical switches. Asused herein the term “mirror” means a surface that specularly reflects alarge fraction of incident light. As used herein the term “liquidcrystal cell” refers to a structure containing a liquid crystal materialthat is capable of being ordered. One non-limiting example of a liquidcrystal cell element is a liquid crystal display.

Articles can be rendered photochromic with the indeno-fusednaphthopyrans of the present invention by methods including, but notlimited to, imbibition methods, cast-in-place methods, coating methods,in-mold coating methods, over-mold methods, and lamination methods. Withimbibition methods, the indeno-fused naphthopyran is typically diffusedinto a polymeric material of a previously formed or fabricated article,such as a substrate or previously applied coating or film. Imbibitioncan be performed by immersing the polymeric material of a previouslyformed or fabricated article in a solution containing the indeno-fusednaphthopyran, with or without heating. Thereafter, although notrequired, the indeno-fused naphthopyran can be bonded with the polymericmaterial (e.g., of the substrate or coating).

With cast-in-place methods, the indeno-fused naphthopyran can be mixedwith: a polymer and/or oligomer composition in solution or melt form; ormonomer composition in liquid form, so as to form a castablephotochromic composition. The castable photochromic composition is thentypically introduced into the cavity of a mold (e.g., a lens mold). Thecastable photochromic composition is then set (e.g., cured) within themold so as to form a photochromic article.

With articles that include a substrate, the indeno-fused naphthopyransof the present invention can be connected to at least a portion of thesubstrate as part of a coating that is connected to at least a portionof the substrate. The substrate can be a polymeric substrate or aninorganic substrate (such as, but not limited to, a glass substrate).The indeno-fused naphthopyran of the present invention can beincorporated into at least a portion of a coating composition prior toapplication of the coating composition to the substrate. Alternatively,a coating composition can be applied to the substrate, at leastpartially set, and thereafter the indeno-fused naphthopyran of thepresent invention can be imbibed into at least a portion of the coating.As used herein, the terms “set” and “setting” include, withoutlimitation, curing, polymerizing, cross-linking, cooling, and drying.

Photochromic articles can be prepared using the indeno-fusednaphthopyrans of the present invention by art-recognized in-mold coating(or in-mold casting) methods. With in-mold coating methods, aphotochromic coating composition including the indeno-naphthopyran ofthe present invention, which can be a liquid coating composition or apowder coating composition, is applied to at least a portion of theinterior surface of a mold, and then at least partially set. Thereafter,a polymer solution or melt, or oligomeric or monomeric solution ormixture is cast or molded within the mold cavity and in contact with thepreviously applied photochromic coating composition, and at leastpartially set. The resulting photochromic article is then removed fromthe mold. Non-limiting examples of powder coatings in which theindeno-naphthopyrans according to various non-limiting embodimentsdisclosed herein can be employed are set forth in U.S. Pat. No.6,068,797 at col. 7, line 50 to col. 19, line 42, which disclosure ishereby specifically incorporated by reference herein.

Photochromic articles prepared using the indeno-fused naphthopyrans ofthe present invention can also be formed by art-recognized over-moldmethods. Over-mold methods typically involve forming a substrate withina mold, and then forming an interior space between the substrate and aninterior surface of the mold, into which a photochromic coatingcomposition is then subsequently introduced (e.g., injected) and thenset (e.g., cured). Alternatively, over-mold methods can involveintroducing a previously formed substrate into a mold, such that aninterior space is defined between the substrate and an interior moldsurface, and thereafter a photochromic coating composition is introduced(e.g., injected) into the interior space.

Photochromic articles prepared using the indeno-fused naphthopyrans ofthe present invention can also be formed by art-recognized laminationmethods. With lamination methods, a film comprising the indeno-fusednaphthopyrans of the present invention can be adhered or otherwiseconnect to a portion of the substrate, with or without an adhesiveand/or the application of heat and pressure. Thereafter, if desired, asecond substrate can be applied over the first substrate and the twosubstrates can be laminated together (e.g., by the application of heatand pressure) to form an element wherein the film comprising theindeno-fused naphthopyran is interposed between the two substrates.Methods of forming films comprising a photochromic material can includefor example and without limitation, combining a photochromic materialwith a polymeric solution or oligomeric solution or mixture, casting orextruding a film therefrom, and, if required, at least partially settingthe film. Additionally or alternatively, a film can be formed (with orwithout a photochromic material) and imbibed with the photochromicmaterial.

The indeno-fused naphthopyrans prepared by the method of the presentinvention, can be used alone or in combination with other photochromicmaterials. Classes of photochromic materials that can be used incombination (e.g., in mixture) with the indeno-fused naphthopyrans ofthe present invention include, but are not limited to:spiro(indoline)naphthoxazines and spiro(indoline)benzoxazines, forexample as described in U.S. Pat. Nos. 3,562,172, 3,578,602, 4,215,010,4,342,668, 5,405,958, 4,637,698, 4,931,219, 4,816,584, 4,880,667, and4,818,096; benzopyrans, for example as described in U.S. Pat. Nos.3,567,605, 4,826,977, 5,066,818, 4,826,977, 5,066,818, 5,466,398,5,384,077, 5,238,931, and 5,274,132; photochromic organo-metaldithizonates, such as, (arylazo)-thioformic arylhydrazidates, e.g.,mercury dithizonates which are described in, for example, U.S. Pat. No.3,361,706; and fulgides and fulgimides, e.g., the 3-furyl and 3-thienylfulgides and fulgimides which are described in U.S. Pat. No. 4,931,220at column 20, line 5 through column 21, line 38.

The present invention is more particularly described in the followingexamples, which are intended to be illustrative only, since numerousmodifications and variations therein will be apparent to those skilledin the art. Unless otherwise specified, all parts and all percentagesare by weight.

EXAMPLES

In Part 1 of the Examples, the synthesis procedures used to make thenaphthols of Examples 1-3, and the photochromic materials of Examples 1Aand 3A is described. Part 2 describes the photochromic performancetesting and results for photochromic compounds of Examples 1A and 3A.

Part 1: Synthesis of the Naphthols of Examples 1-3 and PhotochromicCompounds of Examples 1A and 3A Example 1 Step 1

Solid maleic anhydride (110 g) was dissolved in cumene (400 mL) in a 1 Lsingle-neck flask, followed by addition of ^(t)butyl peroxide (11 mL).The resulting mixture was heated under refluxing condition for 20 hours.The solvent was removed under reduced pressure. The product was obtainedas viscous brown oil (260 g). The recovered product containing2-(2-phenylpropan-2-yl)succinic acid was used for next step withoutfurther purification.

Step 2

The product from Step 1 (260 g) was dissolved in xylene (500 mL) in a 1L single-neck flask equipped with a Dean-Star Trap and water condenser,followed by addition of dodecyl benzene sulfonic acid (18 g). Theresulting mixture was heated under refluxing condition for 4 hours. Thesolvent was removed under reduced pressure. The product was obtained asviscous brown oil (280 g). The product containing3-(2-phenylpropan-2-yl)dihydrofuran-2,5-dione was used in the next stepwithout purification.

Step 3

The product from Step 2, (280 g), was dissolved in dichloromethane (1.4L) in a 2 L three-neck flask. The resulting mixture was cooled to 0-10°C. with brine-ice mixture. Anhydrous aluminum chloride (330 g) was addedto the mixture slowly through a solid addition funnel. Hydrochloric gasgenerated from the reaction was absorbed by an aqueous potassiumhydroxide solution. The cooling batch was removed 1 hour after theaddition. After another hour the reaction was quenched by pouring intoicy water (2 L) and acidified with hydrochloric acid (12N, 800 mL). Theproduct was extracted with ethyl acetate (2×1 L). The emulsion wasdisrupted by the addition of brine (1 L). The organic layers wererecovered, combined, dried over anhydrous sodium sulfate andconcentrated under reduced pressure to provide product (360 g). Therecovered product was purified by silica gel chromatography using amixture of ethyl acetate/hexanes as eluent to provide the desiredproduct (150 g). NMR showed the product to have a structure consistentwith 2-(1,1-dimethyl-3-oxo-2,3-dihydro-1H-inden-2-yl)acetic acid

Step 4

The product (10 g) from Step 3 and 2-amino-2-methylpropanol (5 g) weredissolved in xylene (45 mL) in a 250 mL one-neck round bottom (RB) flaskwith a Dean-Stark trap and water condenser under a N₂ blanket. Theresulting mixture was heated under refluxing condition for 20 hours. Themixture was then was cooled and purified by silica gel chromatographyusing a mixture of ethyl acetate/hexanes as eluent to provide one majoroily product (6 g). NMR showed the product to have a structureconsistent with2-((4,4-dimethyl-4,5-dihydrooxazol-2-yl)methyl)-3,3-dimethyl-2,3-dihydro-1H-inden-1-one.

Step 5

The oily product from Step 4 was dissolved in anhydrous tetrahydrofuran(40 mL) in a 250 mL one-neck round bottom flask under N₂ blank.Magnesium bromide (4 g) was added to the same flask. The flask wasseated in ice water bath. 3-Methoxyphenyl magnesium bromide intetrahydrofuran solution (40 mL, 1M) was added to the mixture through anadditional funnel over 10 minutes. The ice water bath was removed uponthe addition. The resulting mixture was stirred for 1 hour and thenpoured into ice water. The slurry was acidified by 10% hydrochloric acidsolution and extracted with diethyl ether. The top layer was condensedto provide an oily residue. The residue was dissolved in a mixture ofdioxane and 3N hydrochloric acid solution (50/50 mL) and the resultingmixture was heated under refluxing conditions for 3 hours. The mixturewas cooled and extracted with ethyl acetate. The recovered top layer wasdried over sodium sulfate and concentrated to provide an oily residue.The residue was purified by silica gel chromatography using a mixture ofethyl acetate/hexanes as eluent to provide an oily product (6 g)containing 2-(3-(2-methoxyphenyl)-1,1-dimethyl-1H-inden-2-yl)acetic acidthat was used in the next step without further purification.

Step 6

The product from Step 5 (6 g) was dissolved in acetic anhydride (30 mL)in a 250 mL one-neck round bottom flask under N₂ blank. The resultingsolution was heated under refluxing for 1.5 hour. Bismuth(III)trifluoromethanesulfonate (0.1 g) catalyst was added to the hot mixture.Refluxing was continued for 2 hours. The reaction mixture was cooled andthe pH was reduced 6-7 with potassium hydroxide and sodium bicarbonate.The product was extracted with ethyl acetate and the solution was driedover sodium sulfate. The solvent was stripped off under reducedpressure. The resulting product containing2-methoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-yl acetate was dried undervacuum to provide product (6 g) that was used in next step withoutpurification.

Step 7

The product from Step 6 (6 g) was dissolved in anhydrous methanol (50mL) in a 250 mL one-neck round bottom flask under N₂ blank. Concentratedhydrochloric acid (1 mL) was added to the flask. The resulting solutionwas heated under refluxing for 2 hours. The reaction mixture wascondensed and the residue was purified by silica gel chromatographyusing a mixture of ethyl acetate/hexanes as eluent to provide thedesired product (1.4 g). NMR analysis showed the product to have astructure consistent with 2-methoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-olas shown in the following graphic formula:

Example 1A

The product from Example 1 (1.5 g), was dissolved in dichloromethane (20mL) in a single-necked 100 mL flask, followed by addition of dodecylbenzene sulfonic acid (0.02 g). 1,1-Bis(4-methoxyphenyl)-2-propyn-1-ol(0.7 g) was added to the reaction mixture. The mixture was stirred atroom temperature and monitored by TLC analysis. Upon completion of thereaction, the product was purified by silica gel chromatography using amixture of ethyl acetate/hexanes as eluent. The major product was thenrecrystallized to provide the desired product (1 g). NMR showed theproduct to have a structure consistent with3,3-bis(4-methoxyphenyl)-7-methoxy-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyranas represented by the following graphic formula.

Example 2 Step 1

4-Methoxyphenyl magnesium bromide in tetrahydrofuran (200 mL, 1M) wascharged to a 1 L one-neck round bottom flask through an additionalfunnel under N₂ blank. The product from Step 3 of Example 1,2-(1,1-dimethyl-3-oxo-2,3-dihydro-1H-inden-2-yl)acetic acid (9 g) inanhydrous tetrahydrofuran (60 mL) solution was added dropwise to theGrignard solution over 30 minutes. The reaction mixture was stirred atroom temperature for 20 hours. The mixture was poured into ice water andthe resulting slurry was acidified by the addition of 10% hydrochloricacid (200 mL). The mixture was extracted with ethyl acetate. Therecovered top layer was concentrated to provide the major product (24g). The recovered product and pyridinium p-toluenesulfonate (1 g) weredissolved in toluene (150 mL) in a 500 mL one-neck round bottom flaskwith a Dean-Stark trap and water condenser. The mixture was heated underrefluxing condition for 3 hours. The reaction mixture was condensed toprovide the major product (24 g). The residue was filtered through asilica gel column using a mixture of ethyl acetate/hexanes as eluent toafford the major product (13 g). The recovered product containing24343-methoxyphenyl)-1,1-dimethyl-1H-inden-2-yl)acetic acid was used innext step without further purification.

Step 2

The product from Step 1 (20 g) was dissolved in acetic anhydride (50 mL)in a 500 mL one-neck round bottom flask equipped with water condenserunder N₂ blank. Bismuth(III) trifluoromethanesulfonate (0.1 g) catalystwas added to the mixture. The mixture was heated under refluxingcondition for 6 hours. The mixture was concentrated and the recoveredproduct containing 3-methoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ylacetate was used in next step without further purification.

Step 3

The procedure of Step 7 of Example 1 was followed except that theproduct from Step 2 above was used in place of3-methoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-yl acetate to produce thedesired product. Mass Spectroscopy showed the product to have amolecular weight of 290 which was consistent with the structure of3-methoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ol shown in the followinggraphic formula:

Example 3 Step 1

A 3,5-difluorophenylmagnesium bromide in diethyl ether solution (0.8M,350 mL) was charged to a 2 L two-neck round bottom flask under N₂ blank.The product from Step 3 of Example 1,2-(1,1-dimethyl-3-oxo-2,3-dihydro-1H-inden-2-yl)acetic acid (8 g) inanhydrous tetrahydrofuran (60 mL) solution was added dropwise to theGrignard solution over 30 minutes. The reaction mixture was stirred atroom temperature for 20 hours. The mixture was poured into ice water andthe resulting slurry was acidified with 10% hydrochloric acid solution(300 mL). The mixture was extracted with ethyl acetate. The recoveredtop layer was concentrated to provide product (24 g). The product andpyridinium p-toluenesulfonate (1 g) were dissolved in toluene (100 mL)in a 500 mL one-neck round bottom flask with a Dean-Stark trap and watercondenser. The mixture was heated under refluxing condition for 3 hours.The reaction mixture was then concentrated to provide major product (20g). The recovered product containing2-(3-(2,4-difluorophenyl)-1,1-dimethyl-1H-inden-2-yl)acetic acid wasused in next step without further purification.

Step 2

The product from Step 1 (20 g) was dissolved in acetic anhydride (50 mL)in a 500 mL one-neck round bottom flask equipped with water condenserunder N₂ blank. Bismuth(III) trifluoromethanesulfonate (0.1 g) catalystwas added to the mixture. The mixture was heated under refluxingcondition for 6 hours. The resulting mixture was condensed and therecovered oily product containing2,4-difluoro-7,7-dimethyl-7H-benzo[c]fluoren-5-yl acetate was used innext step without further purification.

Step 3

The product from Step 2 (20 g), was dissolved in methanol (100 mL) in asingle-neck 250 mL round bottom flask, followed by addition ofconcentrated hydrochloric acid (37%, 0.5 mL). The mixture was heatedunder refluxing condition for 3 hours. The solvent was removed underreduced pressure to provide the major product (18 g). The major productwas purified by silica gel chromatography to yield the desired product(10 g). UV Spectroscopy showed the product to have spectral profileconsistent with the structure of2,4-difluoro-7,7-dimethyl-7H-benzo[c]fluoren-5-ol shown in the followinggraphic formula:

Example 3A

The procedure of Example 1A was followed except that the product ofExample 3 was used in place of the product of Example 1 andp-toluenesulfonic acid monohydrate (0.1 g) was used in place of dodecylbenzene sulfonic acid (1 drop). NMR showed the product to have astructure consistent with3,3-bis(4-methoxyphenyl)-5,7-difluoro-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyranas represented by the following graphic formula:

Part 2: Photochromic Performance Testing and Results

The photochromic performance of the photochromic materials of Examples1A and 3A were tested as follows. A quantity of the photochromicmaterial to be tested, calculated to yield a 1.5×10⁻³M solution, wasadded to a flask containing 50 grams of a monomer blend of 4 partsethoxylated bisphenol A dimethacrylate (BPA 2EO DMA), 1 partpoly(ethylene glycol) 600 dimethacrylate, and 0.033 weight percent2,2′-azobis(2-methyl propionitrile) (AIBN). The photochromic materialwas dissolved into the monomer blend by stirring and gentle heating ifnecessary. After a clear solution was obtained, it was vacuum degassedbefore being poured into a flat sheet mold having the interiordimensions of 2.2 mm×6 inches (15.24 cm)×6 inches (15.24 cm). The moldwas sealed and placed in a horizontal air flow, programmable ovenprogrammed to increase the temperature from 40° C. to 95° C. over a 5hour interval, hold the temperature at 95° C. for 3 hours and then lowerit to 60° C. for over a 2 hour interval. After the mold was opened, thepolymer sheet was cut using a utility knife to score the surface andsnap into 2 inch (5.1 cm) test squares.

The photochromic test squares prepared as described above were testedfor photochromic response on an optical bench. Prior to testing on theoptical bench, the photochromic test squares were exposed to 365 nmultraviolet light for about 15 minutes to cause the photochromicmaterial to transform from the ground state-form to an activated-stateform, and then placed in a 75° C. oven for about 15 minutes to allow thephotochromic material to revert back to the ground state-form. The testsquares were then cooled to room temperature, exposed to fluorescentroom lighting for at least 2 hours, and then kept covered (that is, in adark environment) for at least 2 hours prior to testing on an opticalbench maintained at 73° F. (23° C.).

The optical bench fitted with a Schott 3 mm KG-2 band-pass filter,neutral density filter(s) and a Newport Model#67005 300-watt Xenon arclamp with Model#69911 power supply in association with a Newport Model689456 Digital Exposure/Tinier was used to control the intensity of theirradiance beam utilized for activation of the sample. A Uniblitzmodel#CS25S3ZM0 with model#VMM-D3 controller) high-speed computercontrolled shutter, a fused silica condensing lens for beam collimationof this activation lamp beam though a quartz glass water bath samplechamber.

A custom made broadband light source for monitoring responsemeasurements was directed through the sample such that the angle betweenthe activation source and the monitoring beam is 30 degrees with thesample positioned perpendicular to this monitoring beam. This broad beamlight source is obtained by collecting and combining separately filteredlight from a 100-Watt tungsten halogen lamp (controlled by a LambdaUP60-14 constant voltage powder supply) with a split-end, bifurcatedfiber optical cable to enhance the short wavelength light intensity.After passing through the sample, this monitoring light was refocusedinto a 2-inch integrating sphere and fed to an Ocean Optics S2000spectrophotometer by fiber optic cables. Ocean Optics SpectraSuite andPPG proprietary software were used to measure response and control theoperation of the optical bench.

The λ_(max-vis) is the wavelength in the visible spectrum at which themaximum absorption of the activated-state form of the photochromiccompound in a test square occurs. The λ_(max-vis) wavelength wasdetermined by testing the photochromic test squares in a Varian Cary4000 UV-Visible spectrophotometer.

The change in Optical density at saturation for each test sample wasdetermined by opening the shutter from the xenon lamp and measuring thetransmittance after exposing the test chip to 3 W/m² UVA radiation for30 minutes. The change in Optical density at saturation was calculatedusing the formula: ΔOD=log (% Tb/% Ta), where % Tb is the percenttransmittance in the bleached state, % Ta is the percent transmittancein the activated state both at the λ_(max-vis) and the logarithm is tothe base 10. The first fade half life (“T_(1/2)”) or bleach rate is thetime interval in seconds for the absorbance of the activated-state formof the photochromic material in the test squares to reach one half theΔOD at saturation value at room temperature (23° C.), after removal ofthe source of activating light. The Sensitivity (ΔOD/Min) is a measureof how quickly the sample darkens and is calculated from the equationΔOD_(sen)=ΔOD_(5min)×12. The results are listed in Table 1.

TABLE 1 Photochromic Performance Test Results λ_(max-vis) SensitivityΔOD at T½ Example # (nm) (ΔOD/Min) saturation (sec) 1A 546 0.56 1.16 2173A 551 0.55 0.64 73

The present invention has been described with reference to specificdetails of particular embodiments thereof. It is not intended that suchdetails be regarded as limitations upon the scope of the inventionexcept insofar as and to the extent that they are included in theaccompanying claims.

1. A method of making an indeno-fused naphthol represented by Formula I,

wherein, m and n are each independently selected from 0 to 4, R¹ foreach m, and R² for each n, are in each case independently selected fromhydrocarbyl optionally interrupted with at least one of —O—, —S—,—C(O)—, —C(O)O—, —S(O)—, —N(R₁₁′)— where R₁₁′ is selected from hydrogen,hydrocarbyl or substituted hydrocarbyl, and combinations of two or morethereof; substituted hydrocarbyl optionally interrupted with at leastone of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N(R₁₁′)— where R₁₁′ isselected from hydrogen, hydrocarbyl or substituted hydrocarbyl, andcombinations of two or more thereof; halogen; cyano; and —N(R₁₁′)R₁₂′,wherein R₁₁′ and R₁₂′ are each independently selected from hydrogen,hydrocarbyl or substituted hydrocarbyl, or R₁₁′ and R₁₂′ together form aring structure optionally including at least one heteroatom, and R^(g)and R^(h) are each independently selected from, hydrogen; hydrocarbyloptionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—,—S(O)—, —SO₂—, and —N(R₁₁′)— where R₁₁′ is selected from hydrogen,hydrocarbyl or substituted hydrocarbyl; and substituted hydrocarbyloptionally interrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—,—S(O)—, —SO₂—, and —N(R₁₁′)— where R₁₁′ is selected from hydrogen,hydrocarbyl or substituted hydrocarbyl, or R^(g) and R^(h) together forma ring structure optionally including at least one heteroatom, saidmethod comprising, (a) reacting an alkyl benzene represented by FormulaII with maleic anhydride, thereby forming a succinic acid substitutedintermediate represented by Formula III,

(b) converting the succinic-acid substituted intermediate represented byFormula III to a succinic anhydride substituted intermediate representedby Formula IV,

(c) converting the succinic anhydride substituted intermediaterepresented by Formula IV to an indanone acid intermediate representedby Formula V,

(d) reacting the indanone acid intermediate represented by Formula Vwith a nucleophile represented by Formula VI to form a substitutedindanone intermediate represented by at least one of Formula VIIa,Formula VIIb and Formula VIIc,

wherein M represents a counterion comprising a metal selected from Mg,Li, Cu and combinations thereof,

(e) converting said substituted indanone intermediate represented by atleast one of Formula VIIa, Formula VIIb and Formula VIIc to saidindeno-fused naphthol represented by Formula I.
 2. The method of claim 1further comprising, converting said indanone acid intermediaterepresented by Formula V to an indanone oxazoline intermediaterepresented by Formula VIII,

wherein R⁴ and R⁵ are each independently selected from hydrogen,hydrocarbyl and substituted hydrocarbyl, reacting the indanone oxazolineintermediate represented by Formula VIII with said nucleophilerepresented by Formula VI to form a substituted indanone oxazolineintermediate represented by at least one of Formula IXa and IXb,

converting the substituted indanone oxazoline intermediate representedby at least one of Formula IXa and IXb to said substituted indanoneintermediate represented by at least one of Formula VIIa, Formula VIIband Formula VIIc, and converting said substituted indanone intermediaterepresented by at least one of Formula VIIa, Formula VIIb and FormulaVIIc to said indeno-fused naphthol represented by Formula I.
 3. Themethod of claim 1, wherein reacting said alkyl benzene represented byFormula II with maleic anhydride, is performed in the presence of abishydrocarbyl peroxide.
 4. The method of claim 1, wherein conversion ofthe said succinic anhydride substituted intermediate represented byFormula IV to said indanone acid intermediate represented by Formula V,is performed in the presence of an acid.
 5. The method of claim 4,wherein said acid is selected from aluminum chloride, tin chloride,bismuth tris-triflate, one or more phosphoric acids, and combinationsthereof.
 6. The method of claim 1, wherein conversion of said indanoneintermediate represented by at least one of Formula VIIa, Formula VIIband Formula VIIc to said indeno-fused naphthol represented by Formula I,is conducted in the presence of a material selected from carboxylic acidhalide, carboxylic acid anhydride, sulfonyl halide and combinationsthereof, thereby forming an indeno-fused naphtho-intermediaterepresented by the following Formula X,

wherein R¹⁴ is selected from —C(O)—R¹⁵ and —S(O)(O)R¹⁵, wherein R¹⁵ isselected from hydrocarbyl and halohydrocarbyl, and reacting saidindeno-fused naphtho-intermediate represented by Formula X with aBrønsted acid, thereby forming said indeno-fused naphthol represented byFormula I.
 7. The method of claim 1, wherein conversion of said indanoneintermediate represented by at least one of Formula VIIa, Formula VIIband Formula VIIc to said indeno-fused naphthol represented by Formula I,is conducted in the presence of a Brønsted acid.
 8. The method of claim7, wherein said Brønsted acid is selected from carboxylic acids,sulfonic acids, phosphoric acids, and combinations thereof.
 9. Themethod of claim 1, wherein for the indeno-fused naphthol represented byFormula I, R¹ for each m, and R² for each n, are in each caseindependently selected from, a reactive substituent; a compatiblizingsubstituent; halogen selected from fluoro and chloro; C₁-C₆ alkyl; C₃-C₇cycloalkyl; substituted or unsubstituted phenyl, the phenyl substituentsbeing selected from hydroxyl, halogen, carbonyl, C₁-C₆ alkoxycarbonyl,cyano, halo(C₁-C₆)alkyl, C₁-C₆ alkyl or C₁-C₆ alkoxy; —O—R₁₀′ or—C(O)—R₁₀′ or —C(O)—OR₁₀′, wherein R₁₀′ is hydrogen, C₁-C₆ alkyl,phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkyl substituted phenyl(C₁-C₃)alkyl,mono(C₁-C₆)alkoxy substituted phenyl(C₁-C₃)alkyl,(C₁-C₆)alkoxy(C₂-C₄)alkyl, C₃-C₇ cycloalkyl, or mono(C₁-C₄)alkylsubstituted C₃-C₇ cycloalkyl; —N(R₁₁′)R₁₂ ¹, wherein R₁₁′ and R₁₂′ areeach independently hydrogen, C₁-C₈ alkyl, phenyl, naphthyl, furanyl,benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl,fluorenyl, C₁-C₈ alkylaryl, C₃-C₂₀ cycloalkyl, C₄-C₂₀ bicycloalkyl,C₅-C₂₀ tricycloalkyl or C₁-C₂₀ alkoxyalkyl, wherein said aryl group isphenyl or naphthyl, or R₁₁′ and R₁₂′ come together with the nitrogenatom to form a C₃-C₂₀ hetero-bicycloalkyl ring or a C₄-C₂₀hetero-tricycloalkyl ring; a nitrogen containing ring represented by thefollowing graphic formula XIIIA,

wherein each —Y— is independently chosen for each occurrence from—C(R₁₃′)₂—, —CH(aryl)-, —C(aryl)₂-, and —C(R₁₃′)(aryl)-, and Z is —Y—,—O—, —S—, —S(O)—, —SO₂—, —NH—, —N(R₁₃′)-, or —N(aryl)-, wherein eachR₁₃′ is independently C₁-C₆ alkyl, each aryl is independently phenyl ornaphthyl, m is an integer 1, 2 or 3, and p is an integer 0, 1, 2, or 3and provided that when p is 0, Z is —Y—; a group represented by one ofthe following graphic formulae XIIIB or XIIIC,

wherein R₁₅, R₁₆, and R₁₇ are each independently hydrogen, C₁-C₆ alkyl,phenyl, or naphthyl, or the groups R₁₅ and R₁₆ together form a ring of 5to 8 carbon atoms and each R^(d) is independently for each occurrenceselected from C₁-C₆ alkyl, C₁-C₆ alkoxy, fluoro or chloro, and Q is aninteger 0, I, 2, or 3; and unsubstituted, mono-, or di-substitutedC₄-C₁₈ spirobicyclic amine, or unsubstituted, mono-, and di-substitutedC₄-C₁₈ spirotricyclic amine, wherein said substituents are independentlyaryl, C₁-C₆ alkyl, C₁-C₆ alkoxy, or phenyl(C₁-C₆)alkyl; or two adjacentR¹ groups, or two adjacent R² groups, independently together form agroup represented by one of XIIID and XIIIE:

wherein T and T′ are each independently oxygen or the group —NR₁₁′-,where R₁₁′, R₁₅, and R₁₆ are as set forth above; and R^(g) and R^(h) areeach independently selected from, (i) hydrogen, C₁-C₈ alkyl, C₁-C₈haloalkyl, C₃-C₇ cycloalkyl, allyl, benzyl, or mono-substituted benzyl,said benzyl substituents being chosen from halogen, C₁-C₆ alkyl or C₁-C₆alkoxy; (ii) an unsubstituted, mono- di-or tri-substituted group chosenfrom phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl,benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl,carbazolyl, or indolyl, said group substituents in being chosen fromhalogen, C₁-C₆ alkyl or C₁-C₆ alkoxy; (iii) mono-substituted phenyl,said substituent located at the para position being —(CH₂)_(t)— or—O—(CH₂)_(t)—, wherein t is the integer 1, 2, 3, 4, 5 or 6, saidsubstituent being connected to an aryl group which is a member of aphotochromic material; (iv) the group —CH(R¹⁰)G, wherein R¹⁰ ishydrogen, C₁-C₆ alkyl or the unsubstituted, mono- or di-substituted arylgroups phenyl or naphthyl, and G is —CH₂OR¹¹, wherein R¹¹ is hydrogen,—C(O)R¹⁰, C₁-C₆ alkyl, C₁-C₃ alkoxy(C₁-C₆)alkyl, phenyl(C₁-C₃)alkyl,mono(C₁-C₆)alkoxy substituted phenyl(C₁-C₃)alkyl, or the unsubstituted,mono- or di-substituted aryl groups phenyl or naphthyl, each of saidphenyl and naphthyl group substituents being C₁-C₆ alkyl or C₁-C₆alkoxy; or (v) R^(g) and R^(h) together form a spiro substituentselected from a substituted or unsubstituted spiro-carbocyclic ringcontaining 3 to 6 carbon atoms, a substituted or unsubstitutedspiro-heterocyclic ring containing 1 or 2 oxygen atoms and 3 to 6 carbonatoms including the spirocarbon atom, said spiro-carbocyclic ring andspiro-heterocyclic ring being annellated with 0, 1 or 2 benzene rings,said substituents being hydrogen or C₁-C₂₀ alkyl.
 10. The method ofclaim 9, wherein, R¹ for each m, and R² for each n, are in each caseindependently selected from unsubstituted phenyl, substituted phenyl,C₁-C₆ alkyl, C₃-C₇ cycloalkyl, C₁-C₈ haloalkyl, fluoro, chloro, and—O—R₁₀′, and R^(g) and R^(h) are each independently selected fromhydrogen, C₁-C₈ alkyl, C₁-C₈ haloalkyl, and C₃-C₇ cycloalkyl, or R^(g)and R^(h) together form a spiro substituent selected from a substitutedor unsubstituted spiro-carbocyclic ring containing 3 to 6 carbon atoms.11. A method of making an indeno-fused naphthopyran represented by thefollowing Formula XI,

wherein, m and n are each independently selected from 0 to 4, R¹ foreach m, and R² for each n, are in each case independently selected fromhydrocarbyl optionally interrupted with at least one of —O—, —S—,—C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N(R₁₁′)— where R₁₁′ is selected fromhydrogen, hydrocarbyl or substituted hydrocarbyl, and combinations oftwo or more thereof; substituted hydrocarbyl optionally interrupted withat least one of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, —N(R₁₁′)—where R₁₁′ is selected from hydrogen, hydrocarbyl or substitutedhydrocarbyl, and combinations of two or more thereof; halogen; cyano;—O—R₁₀′ or —C(O)—R₁₀′ or —C(O)—OR₁₀′, wherein each R₁₀′ is independentlyselected from hydrogen, hydrocarbyl or substituted hydrocarbyl; and—N(R₁₁′)R₁₂′, wherein R₁₁′ and R₁₂′ are each independently selected fromhydrogen, hydrocarbyl or substituted hydrocarbyl, or R₁₁′ and R₁₂′together form a ring structure optionally including at least oneheteroatom, and R^(g) and R^(h) are each independently selected from,hydrogen; hydrocarbyl optionally interrupted with at least one of —O—,—S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, and —N(R₁₁′)— where R₁₁′ isselected from hydrogen, hydrocarbyl or substituted hydrocarbyl; andsubstituted hydrocarbyl optionally interrupted with at least one of —O—,—S—, —C(O)—, —C(O)O—, —S(O)—, —SO₂—, and —N(R₁₁′)— where R₁₁′ isselected from hydrogen, hydrocarbyl or substituted hydrocarbyl; or R^(g)and R^(h) together form a ring structure optionally including at leastone heteroatom, and B and B′ are each independently selected fromunsubstituted aryl, substituted aryl, unsubstituted heteroaryl,substituted heteroaryl, polyalkoxy, and polyalkoxy having apolymerizable group, or B and B′ taken together form a ring structureselected from unsubstituted fluoren-9-ylidene, substitutedfluoren-9-ylidene, saturated spiro-monocyclic hydrocarbon ring,saturated spiro-bicyclic hydrocarbon ring, and spiro-tricyclichydrocarbon ring, said method comprising, (a) reacting an alkyl benzenerepresented by Formula II with maleic anhydride, thereby forming asuccinic acid substituted intermediate represented by Formula III,

(b) converting the succinic acid substituted intermediate represented byFormula III to a succinic anhydride substituted intermediate representedby Formula IV,

(c) converting the succinic anhydride substituted intermediaterepresented by Formula IV to an indanone acid intermediate representedby Formula V,

(d) reacting the indanone acid intermediate represented by Formula Vwith a nucleophile represented by Formula VI to form a substitutedindanone intermediate represented by at least one of Formula VIIa,Formula VIIb and Formula VIIc,

wherein M represents a counterion comprising a metal selected from Mg,Li, Cu and combinations thereof,

(e) converting said substituted indanone intermediate represented by atleast one of Formula VIIa, Formula VIIb and Formula VIIc to anindeno-fused naphthol represented by Formula I,

and (f) reacting the indeno-fused naphthol represented by Formula I witha propargyl alcohol represented by Formula XII, thereby forming saidindeno-fused naphthopyran represented by Formula XI,


12. The method of claim 11, wherein reacting said alkyl benzenerepresented by Formula II with maleic anhydride, is performed in thepresence of a bishydrocarbyl peroxide.
 13. The method of claim 11,wherein conversion of the said succinic anhydride substitutedintermediate represented by Formula IV to said indanone acidintermediate represented by Formula V, is performed in the presence of aLewis acid.
 14. The method of claim 13, wherein said Lewis acid isAlCl₃.
 15. The method of claim 11, wherein conversion of said indanoneintermediate represented by at least one of Formula VIIa, Formula VIIband Formula VIIc to said indeno-fused naphthol represented by Formula I,is conducted in the presence of a material selected from carboxylic acidhalide, carboxylic acid anhydride, sulfonyl halide and combinationsthereof, thereby forming an indeno-fused naphtho-intermediaterepresented by the following Formula X,

wherein R¹⁴ is selected from —C(O)—R⁵ and —S(O)(O)R¹⁵, wherein R¹⁵ isselected from hydrocarbyl and halohydrocarbyl, and reacting saidindeno-fused naphtho-intermediate represented by Formula X with aBrønsted acid, thereby forming said indeno-fused naphthol represented byFormula I.
 16. The method of claim 11, wherein conversion of saidindanone intermediate represented by at least one of Formula VIIa,Formula VIIb and Formula VIIc to said indeno-fused naphthol representedby Formula I, is conducted in the presence of a Brønsted acid.
 17. Themethod of claim 16, wherein said Brønsted acid is selected fromcarboxylic acids, sulfonic acids, phosphoric acids, and combinationsthereof.
 18. The method of claim 11, wherein, R¹ for each m, and R² foreach n, are in each case independently selected from, a reactivesubstituent; a compatiblizing substituent; halogen selected from fluoroand chloro; C₁-C₆ alkyl; C₃-C₇ cycloalkyl; substituted or unsubstitutedphenyl, the phenyl substituents being selected from hydroxyl, halogen,carbonyl, C₁-C₆ alkoxycarbonyl, cyano, halo(C₁-C₆)alkyl, C₁-C₆ alkyl orC₁-C₆ alkoxy; —O—R₁₀′ or —C(O)—R₁₀′ or —C(O)—OR₁₀′, wherein R₁₀′ ishydrogen, C₁-C₆ alkyl, phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkyl substitutedphenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxy substituted phenyl(C₁-C₃)alkyl,(C₁-C₃-C₇ cycloalkyl, or mono(C₁-C₄)alkyl substituted C₃-C₇ cycloalkyl;—N(R₁₁′)R₁₂′, wherein R₁₁′ and R₁₂′ are each independently hydrogen,C₁-C₈ alkyl, phenyl, naphthyl, furanyl, benzofuran-2-yl,benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl,dibenzofuranyl, dibenzothienyl, benzopyridyl, fluorenyl, C₁-C₈alkylaryl, C₃-C₂₀ cycloalkyl, C₄-C₂₀ bicycloalkyl, C₅-C₂₀ tricycloalkylor C₁-C₂₀ alkoxyalkyl, wherein said aryl group is phenyl or naphthyl, orR₁₁′ and R₁₂′ come together with the nitrogen atom to form a C₃-C₂₀hetero-bicycloalkyl ring or a C₄-C₂₀ hetero-tricycloalkyl ring; anitrogen containing ring represented by the following graphic formulaXIIIA,

wherein each —Y— is independently chosen for each occurrence from —CH₂—,—CH(R₁₃′)—, —C(R₁₃′)₂—, —CH(aryl)-, —C(aryl)₂-, and —C(R₁₃′)(aryl)-, andZ is —Y—, —O—, —S—, —S(O)—, —SO₂—, —NH—, —N(R₁₃′)-, or —N(aryl)-,wherein each R₁₃′ is independently C₁-C₆ alkyl, each aryl isindependently phenyl or naphthyl, m is an integer 1, 2 or 3, and p is aninteger 0, 1, 2, or 3 and provided that when p is 0, Z is —Y—; a grouprepresented by one of the following graphic formulae XIIIB or XIIIC,

wherein R₁₅, R₁₆, and R₁₇ are each independently hydrogen, C₁-C₆ alkyl,phenyl, or naphthyl, or the groups R₁₅ and R₁₆ together form a ring of 5to 8 carbon atoms and each R^(d) is independently for each occurrenceselected from C₁-C₆ alkyl, C₁-C₆ alkoxy, fluoro or chloro, and Q is aninteger 0, 1, 2, or 3; and unsubstituted, mono-, or di-substitutedC₄-C₁₈ spirobicyclic amine, or unsubstituted, mono-, and di-substitutedC₄-C₁₈ spirotricyclic amine, wherein said substituents are independentlyaryl, C₁-C₆ alkyl, C₁-C₆ alkoxy, or phenyl(C₁-C₆)alkyl; or two adjacentR groups, or two adjacent R² groups, independently together form a grouprepresented by one of XIIID and XIIIE:

wherein T and T′ are each independently oxygen or the group —NR₁₁′—,where R₁₁′, R₁₅, and R₁₆ are as set forth above; R^(g) and R^(h) areeach independently selected from, (i) hydrogen, C₁-C₈ alkyl, C₁-C₈haloalkyl, C₃-C₇ cycloalkyl, allyl, benzyl, or mono-substituted benzyl,said benzyl substituents being chosen from halogen, C₁-C₆ alkyl or C₁-C₆alkoxy; (ii) an unsubstituted, mono- di-or tri-substituted group chosenfrom phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl,benzofuranyl, thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl,carbazolyl, or indolyl, said group substituents in being chosen fromhalogen, C₁-C₆ alkyl or C₁-C₆ alkoxy; (iii) mono-substituted phenyl,said substituent located at the para position being —(CH₂)_(t)— or—O—(CH₂)_(t)—, wherein t is the integer 1, 2, 3, 4, 5 or 6, saidsubstituent being connected to an aryl group which is a member of aphotochromic material; (iv) the group —CH(R¹⁰)G, wherein R¹⁰ ishydrogen, C₁-C₆ alkyl or the unsubstituted, mono- or di-substituted arylgroups phenyl or naphthyl, and G is —CH₂OR¹¹, wherein R¹¹ is hydrogen,—C(O)R¹⁰, C₁-C₆ alkyl, C₁-C₃ alkoxy(C₁-C₆)alkyl, phenyl(C₁-C₃)alkyl,mono(C₁-C₆)alkoxy substituted phenyl(C₁-C₃)alkyl, or the unsubstituted,mono- or di-substituted aryl groups phenyl or naphthyl, each of saidphenyl and naphthyl group substituents being C₁-C₆ alkyl or C₁-C₆alkoxy; or (v) R^(g) and R^(h) together form a spiro substituentselected from a substituted or unsubstituted spiro-carbocyclic ringcontaining 3 to 6 carbon atoms, a substituted or unsubstitutedspiro-heterocyclic ring containing 1 or 2 oxygen atoms and 3 to 6 carbonatoms including the spirocarbon atom, said spiro-carbocyclic ring andspiro-heterocyclic ring being annellated with 0, 1 or 2 benzene rings,said substituents being hydrogen or C₁-C₂₀ alkyl; and B and B′ are eachindependently: an aryl group that is mono-substituted with a reactivesubstituent or a compatiblizing substituent; a substituted phenyl; asubstituted aryl; a substituted 9-julolindinyl; a substitutedheteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yl,benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl,dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl, andfluorenyl, wherein the phenyl, aryl, 9-julolindinyl, or heteroaromaticsubstituent is the reactive substituent R; an unsubstituted, mono-, di-,or tri-substituted phenyl or aryl group; 9-julolidinyl; or anunsubstituted, mono- or di-substituted heteroaromatic group chosen frompyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl,carbazoyl, benzopyridyl, indolinyl, and fluorenyl, wherein each of thephenyl, aryl and heteroaromatic substituents are each independently:hydroxyl, a group —C(═O)R₂₁, wherein R₂₁ is —OR₂₂, —N(R₂₃)R₂₄,piperidino, or morpholino, wherein R₂₂ is allyl, C₁-C₆ alkyl, phenyl,mono(C₁-C₆)alkyl substituted phenyl, mono(C₁-C₆)alkoxy substitutedphenyl, phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkyl substitutedphenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxy substituted phenyl(C₁-C₃)alkyl,C₁-C₆ alkoxy(C₂-C₄)alkyl or C₁-C₆ haloalkyl, R₂₃ and R₂₄ are eachindependently C₁-C₆ alkyl, C₅-C₇ cycloalkyl, phenyl or substitutedphenyl, the phenyl substituents being C₁-C₆ alkyl or C₁-C₆ alkoxy, andsaid halo substituent is chloro or fluoro, aryl, mono(C₁-C₁₂)alkoxyaryl,di(C₁-C₁₂)alkoxyaryl, mono(C₁-C₁₂)alkylaryl, di(C₁-C₁₂)alkylaryl,haloaryl, C₃-C₇ cycloalkylaryl, C₃-C₇ cycloalkyl, C₃-C₇ cycloalkyloxy,C₃-C₇ cycloalkyloxy(C₁-C₁₂)alkyl, C₃-C₇ cycloalkyloxy(C₁-C₁₂)alkoxy,aryl(C₁-C₁₂)alkyl, aryl(C₁-C₁₂)alkoxy, aryloxy, aryloxy(C₁-C₁₂)alkyl,aryloxy(C₁-C₁₂)alkoxy, mono- or di(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkyl, mono-or di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkyl, mono- ordi-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkoxy, mono- ordi-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkoxy, amino, mono- ordi-(C₁-C₁₂)alkylamino, diarylamino, piperazino,N—(C₁-C₁₂)alkylpiperazino, N-arylpiperazino, aziridino, indolino,piperidino, morpholino, thiomorpholino, tetrahydroquinolino,tetrahydroisoquinolino, pyrrolidyl, C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl,C₁-C₁₂ alkoxy, mono(C₁-C₁₂)alkoxy(C₁-C₁₂)alkyl, acryloxy, methacryloxy,or halogen; an unsubstituted or mono-substituted group chosen frompyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolinyl,phenothiazinyl, phenoxazinyl, phenazinyl, and acridinyl, each of saidsubstituents being C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, phenyl, or halogen; agroup represented by one of:

wherein K is —CH₂— or —O—, and Φ is —O— or substituted nitrogen,provided that when Φ is substituted nitrogen, K is the substitutednitrogen substituents being hydrogen, C₁-C₁₂ alkyl, or C₁-C₁₂ acyl, eachR₂₅ being independently chosen for each occurrence from C₁-C₁₂ alkyl,C₁-C₁₂ alkoxy, hydroxy, and halogen, R₂₆ and R₂₇ each beingindependently hydrogen or C₁-C₁₂ alkyl, and u is an integer ranging from0 to 2; or a group represented by:

wherein R₂₈ is hydrogen or C₁-C₁₂ alkyl, and R₂₉ is an unsubstituted,mono-, or di-substituted group chosen from naphthyl, phenyl, furanyl,and thienyl, wherein the substituents are C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy,or halogen; or B and B′ taken together form one of a fluoren-9-ylidene,mono-, or di-substituted fluoren-9-ylidene, each of saidfluoren-9-ylidene substituents being independently chosen from C₁-C₁₂alkyl, C₁-C₁₂ alkoxy, and halogen.
 19. The method of claim 18, wherein,R¹ for each m, and R² for each n, are in each case independentlyselected from unsubstituted phenyl, substituted phenyl, C₁-C₆ alkyl,C₃-C₇ cycloalkyl, C₁-C₈ haloalkyl, fluoro, chloro, and —O—R₁₀′, R^(g)and R^(h) are each independently selected from hydrogen, C₁-C₈ alkyl,C₁-C₈ haloalkyl, and C₃-C₇ cycloalkyl, or R^(g) and R^(h) together forma Spiro substituent selected from a substituted or unsubstitutedspiro-carbocyclic ring containing 3 to 6 carbon atoms, and B and B′ areeach independently selected from aryl substituted with C₁-C₆ alkoxy, andaryl substituted with morpholino.